Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\\n\\n
Seeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\\n\\n
Over these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\\n\\n
We are excited about the present, and we look forward to sharing many more successes in the future.
\\n\\n
Thank you all for being part of the journey. 5,000 times thank you!
\\n\\n
Now with 5,000 titles available Open Access, which one will you read next?
Preparation of Space Experiments edited by international leading expert Dr. Vladimir Pletser, Director of Space Training Operations at Blue Abyss is the 5,000th Open Access book published by IntechOpen and our milestone publication!
\n\n
"This book presents some of the current trends in space microgravity research. The eleven chapters introduce various facets of space research in physical sciences, human physiology and technology developed using the microgravity environment not only to improve our fundamental understanding in these domains but also to adapt this new knowledge for application on earth." says the editor. Listen what else Dr. Pletser has to say...
\n\n\n\n
Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\n\n
Seeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\n\n
Over these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\n\n
We are excited about the present, and we look forward to sharing many more successes in the future.
\n\n
Thank you all for being part of the journey. 5,000 times thank you!
\n\n
Now with 5,000 titles available Open Access, which one will you read next?
\n'}],latestNews:[{slug:"stanford-university-identifies-top-2-scientists-over-1-000-are-intechopen-authors-and-editors-20210122",title:"Stanford University Identifies Top 2% Scientists, Over 1,000 are IntechOpen Authors and Editors"},{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"},{slug:"all-intechopen-books-available-on-perlego-20201215",title:"All IntechOpen Books Available on Perlego"},{slug:"oiv-awards-recognizes-intechopen-s-editors-20201127",title:"OIV Awards Recognizes IntechOpen's Editors"},{slug:"intechopen-joins-crossref-s-initiative-for-open-abstracts-i4oa-to-boost-the-discovery-of-research-20201005",title:"IntechOpen joins Crossref's Initiative for Open Abstracts (I4OA) to Boost the Discovery of Research"},{slug:"intechopen-hits-milestone-5-000-open-access-books-published-20200908",title:"IntechOpen hits milestone: 5,000 Open Access books published!"},{slug:"intechopen-books-hosted-on-the-mathworks-book-program-20200819",title:"IntechOpen Books Hosted on the MathWorks Book Program"}]},book:{item:{type:"book",id:"7796",leadTitle:null,fullTitle:"Human 4.0 - From Biology to Cybernetic",title:"Human 4.0",subtitle:"From Biology to Cybernetic",reviewType:"peer-reviewed",abstract:"Information technology is becoming ingrained in our everyday life. 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1. Introduction
Proton exchange membrane fuel cells (PEMFCs), as an important alternative energy source with great potentials for use in applications ranging from cellular phones, laptops, digital camera and other conventionally battery driven devices to long-term stationary monitoring electronics, have been extensively investigated (K. Matsumoto et al., 2009; P. Xing et al., 2004). In a PEMFC, the conversion of chemical energy to electrical energy occurs via a direct electrochemical reaction, and its efficiency is directly dependent upon the catalysts used (X. Wang et al., 2004). To be commercially viable, it is generally required that these catalysts have high durability, low cost and higher activities in oxygen reduction and/or fuel oxidation reaction (Kundu et al., 2009). Currently, the most widely used catalysts in the PEMFCs are metal nanoparticles (NPs), mainly Pt and/or Pt based alloys (W.Z. Li et al., 2002, 2003, 2004; Prabhuram et al., 2006; X. Wang et al., 2005). These metal NPs are usually characterized with high activities in oxygen reduction and/or fuel oxidation reaction due to their high surface to volume ratio and improved Fermi levels for redox reactions (W.Z. Li et al., 2006; S.Y. Wang et al., 2009; B.H. Wu et al., 2009; Y. Zhao et al., 2007). However, individual metal NPs are usually unstable and prone to loss of their catalytic activity due to their irreversible aggregation during the electrochemical processes. For practical uses, therefore, specific supports are mostly used to mobilize and prevent these metal NPs from aggregation.
Among various types of supports, carbon nanotubes (CNTs) are undoubtedly the most widely used. CNTs are allotropes of carbon with a cylindrical nanostructure, and are characterized as elongated fullerenes with diameters ranging from 1-100 nm (Wunderlich, 2007) and lengths of up to several microns. They can be single walled (called as single walled CNTs, SWCNTs) or multiple walled (called as multiple walled CNTs, MWCNTs) (Cassell et al., 1999; Iijima, 1991; Ijima & Ichihashi, 1993; Journet et al., 1997; Thess et al., 1996). These cylindrical carbon molecules have unique properties, such as high-surface area, good electronic conductivity, strong mechanical properties and high-chemical stability, which make them potentially useful in many applications in nanotechnology, electronics, optics, and other fields of materials science, as well as potential uses in architectural fields (Baughman et al., 2002; Pham-Huu et al., 2002). Studies have shown that the deposition of metal NPs onto the surface of CNTs can not only protect these particles from aggregation, but also improve their catalytic activities, and even produce properties that are not accessible to CNTs and metal NPs alone, which are important for their use in PEMFCs (W.Z. Li et al., 2006; S.Y. Wang et al., 2009; B.H. Wu et al., 2009; Y. Zhao et al., 2007). However, due to the inertness of the CNT walls, the effective attachment of metal catalysts remains a challenge, especially for the solution-based methods for the preparation of metal deposited CNTs (metal/CNTs) (Balasubramanian & Burghard, 2005). Surface functionalization of CNTs is, therefore, generally required to enable a homogeneous and uniform deposition of metal NPs (J. Chen et al., 1998; Yu et al., 1998). It is, however, demonstrated that the surface functionalization methods have great influence on the structure and properties of CNTs. In some cases, harsh chemical or electrochemical oxidations applied with concentrated strong acid could lead to a structural destruction to CNTs, resulting in decrease in their electrical conductivity and correspondingly a possible reduction in the catalytic activity of the obtained metal/CNTs when used in PEMFCs (Koshio et al., 2001; J. Li et al., 1998; Qu et al., 2005, 2006). For rational design of metal/CNTs catalysts, it is therefore important to well understand the various methods used for the CNT functionalization.
Except for the methods used for the CNT functionalization, the catalytic activity of the metal/CNTs is also affected by the size and distribution of deposited metal NPs. Since the dispersion and particle size of metal NPs largely determine the utilization and catalytic activity of metal/CNTs, the synthesis of metal NPs supported by CNTs with a controlled manner is of fundamental and practical importance. Indeed, researches have demonstrated that the deposition, distribution, and crystalline size of metal NPs supported on CNTs are significantly dependent upon the method used to synthesize metal/CNTs, the types of functional groups on the surface of metal NPs, and the way that metal NPs are adsorbed. It is therefore necessary to well know about the various methods used to synthesize metal/CNTs for the preparation of catalysts of high efficiency.
In the chapter, we will first provide brief recapitulations of the concepts of various surface functionalization methods of CNTs, and some possible shortcomings associated with these methods. This is followed by descriptions of the various methods used for the preparation of metal/CNTs, and the way that the metal ions and metal NPs are adsorbed onto CNTs is also elucidated. For the activity validation of the synthesized catalysts, it is essential to directly use them in fuel cells. It is demonstrated that the performance of the catalysts in the fuel cell is also affected by the methods for synthesis of membrane electrode assembly (MEA), which is the core of a fuel cell. Thus, the activity validation of the synthesized catalysts and the methods used for the synthesis of MEAs are also described and discussed in this chapter.
2. Methods for functionalization of CNTs
Over the years, a great deal of research has been conducted on the surface modification of CNTs (Hirsch, 2002; Y. Lin et al., 2004; Tasis et al., 2006). The modification of these quasi one-dimensional structures can be carried out by the covalent attachment of chemical groups through reactions onto the π-conjugated skeleton of CNT or by the noncovalent adsorption or wrapping of various functional molecules (Saha & Kundu, 2010). Covalent surface modification of the CNTs leads to a permanent change to the CNT surface. In this case, the CNTs are functionalized with reactive groups which can later form covalent bonds with another molecule (Hirsch, 2002; Tasis et al., 2006). Non-covalent surface modification does not involve the formal chemical bond formation between a molecule and the surface of CNT. The functionalization of CNTs is through adsorption of functional molecules via van der Waals forces, electrostatic forces, hydrogen bonding, or other attractive forces (Y. Lin et al., 2004). Studies have shown that the stability and catalytic activity of metal/CNT composites are strongly dependent upon the way that the CNTs are functionalized. In this section, various CNT functionalization methods based on covalent and noncovalent surface modifications will be discussed. Specifically, a novel CNT functionalization method based on a plasma treatment is also presented. The plasma surface modification is a newly reported method for the CNT functionalization, which is characterized to be a mild surface modification approach and effectively prevent CNTs from the structural destructions possibly caused by other surface functionalization methods (Jiang et al., 2009, 2011). The obtained metal/CNTs are reported to be with higher catalytic activity in a methanol oxidation. Therefore the plasma surface functionalization method has great potentials for the preparation of metal/CNTs of high efficiency as catalysts. Additionally, nitrogen dopped CNTs (N-CNTs) which show great promises as supports of metal NPs for the PEMFC applications, are also introduced. Due to the presence of N, the N-CNTs are reported to exhibit a strong binding to metals NPs. It can therefore avoid using functionalization processes that might be detrimental to the catalytic properties of the obtained metal/N-CNTs (Maiyalagan et al., 2005).
Oxidation with nitric acid solutions is a simple, effective and commonly used approach to functionalize CNTs, which can lead to the formation of CNTs functionalized with carboxylic acid functions, as well as of lactones, phenols, carbonyls, anhydrides, ethers and quinones (Bambagioni et al., 2009). The oxidation of CNTs occurs primarily on the CHn groups (MWCNT defects), giving rise to the formation of alcohols -OH, then C=O and finally carboxylic acid groups, and the density of the functional groups and subsequently deposited metal NPs are strongly dependent upon the concentration of HNO3 used to treat the CNTs (Bambagioni et al., 2009; Reddy & Ramaprabhu, 2007). Since the oxidation with HNO3 solutions can provide CNTs with a large amount of anchoring sites facilitating the deposition of metal NPs of smaller size with homogeneous dispersion, the subsequent fabricated metal/CNT composites usually exhibit a high efficiency in the PEMFC application. As reported by Han et al. (K.I. Han et al., 2004), the electrocatalysts supported on CNTs functionalized by the HNO3 treatment showed improved activity over a commercially available electrocatalyst, E-TEK.
For a better functionalization of CNTs, some oxidants mixtures are also employed to functionalize CNTs with suitable surface for the deposition of metal NPs. For example, Wei et al. (Wei et al., 2008) used a H2SO4/H2O2 solution to functionalize CNTs. The functionalized MWCNTs were characterized to be terminated with carboxyl groups. Halder et al. (Halder et al., 2009) tried a surface treatment of CNTs by its mixing with a combination of concentrated HNO3 and H2SO4 which gave very good surface functionalization on the wall of CNTs. Liu et al. (Liu et al., 2002) reported a high density of oxygen containing species on the CNT surface by a K2Cr2O7/H2SO4 oxidative treatment.
In general, the oxidative treatment technique can functionalize CNTs with oxygen-containing functional groups on their walls, which could increase the surface binding sites of CNTs, avoid the aggregation of the subsequent deposited metal NPs, improve the dispersion of metal NPs, and reduce the average size of metal NPs deposited. The surface functional groups (e.g., carboxyl, hydroxyl, carbonyl groups) on the oxidized CNTs are mostly concentrated at defects sites or at the end tips of CNTs, where the strain and/or the chemical reactivity are higher. However, such functionalization method is inevitably accompanied with a few problems, such as uneven distribution of the surface functional groups, structural damage, and thus partial loss in electrical conductivity of the CNTs. Additionally, due to the hydrophobic surface of CNTs which makes them tend to form aggregates in polar solvents, the surface oxidation of the CNTs is mostly incomplete. That is because during the functionalization process, the CNTs inside these aggregates may not be attacked by the oxidative agents but remain unmodified. However, to use CNTs as a heterogeneous catalyst support, the entire surface of CNTs needs to be oxidized for functionalization, so that highly dispersed catalysts could be achieved. Although prolonged acid oxidation at higher temperatures could lead to an improvement in the quality of CNT functionalization, this might result in more oxidative damage on the graphene structures, leading to potentially more severe loss in the electric conductivity of the carbon nanomaterials. Therefore, in an effort to prepare highly dispersed, high-loading Pt NPs on CNTs, an effective method of CNT functionalization should be sought.
2.1.2. Photochemical oxidation of CNT surfaces
Compared to the oxidation technique mentioned above, the functionalization of CNTs by a photochemical oxidation of surfaces is a more facile and eco-friendly surface functionalization method. The reaction can be conducted in a gas phase and dry process with zero-emission of liquid wastes, providing CNTs with a large amount of carbonyl and carboxyl groups in a very short period of time. Its high efficiency and adjustability in the CNT functionalization provides an additional advantage to control the chemical and physical properties of CNTs. As reported by Asano et al. (Asano et al., 2006), the functionalization of the CNTs by the photochemical oxidation with a short-wavelength ultraviolet irradiation could produce the CNT surface with a high density of oxygen-containing functional groups. An enhancement of the active surface area and the performance of methanol oxidation for the Pt NPs deposited on the photochemical oxidized CNTs, which was attributed to the high dispersion and dense deposition of Pt NPs on the oxygen groups-rich surface, was demonstrated by Jang et al (Jang et al., 2009).
2.1.3. Sonochemical treatment
Sonochemical treatment is reported to be a relatively mild surface modification technique, which can alleviate the damage of CNTs possibly caused by the higher temperature oxidation to a certain extent. During a sonochemical surface modification process, the ultrasonic waves can produce microscopic bubbles in the liquid. A collapsing of these microscopic bubbles results in shock waves, which produce dangling bonds on the surface of CNTs that undergo further chemical reactions and provide the oxidative power to incorporate acidic sites. It is found that the sonochemical treatment of CNTs under acidic aqueous solution (HNO3 and/or H2SO4) conditions can provide CNTs functionalized with –C=O, -C-O-C-, -COO-, and –C-OH groups, which is important for the deposition of uniformly dispersed Pt NPs. The ability to produce CNTs with high densities of functional groups for high loading deposition of metal NPs on CNTs using the sonochemical technique makes it a promising way for the CNT functionalization. Reddy and Ramaprabhu (Reddy & Ramaprabhu, 2007) functionalized the purified SWCNTs by an ultrasonication of CNTs in concentrated nitric acid. The lower power was used to reduce the damage to CNTs during the ultrasonication. The treated CNTs with less structural damage were characterized to be functionalized with high concentrations of -OH and -COOH (Rajalakshmi et al., 2005). Xing et al. (Y.C. Xing et al., 20042005,) have shown that the Pt NPs deposited on sonochemically treated CNTs exhibited a much higher catalytic activity than those supported on the carbon black when used in the PEMFCs. This enhancement of electrochemical activity is attributed to the unique structures of CNTs and the strong interactions between the Pt NPs and the CNT support (Y.C. Xing, 2005).
2.1.4. Silane-assisted method
Several recent reports show that CNTs can be chemically functionalized by silane coupling agents (Kamavarama et al., 2009; Ma et al., 2006; X. Sun et al., 2003; Villers et al., 2006). In the silane assisted functionalization approach, CNTs are mixed with a solution containing a silane derivative and water in ethanol. Upon hydrolysis, the silane derivative form an acid silicate on the surface of CNTs, permitting the exchange of H+ by the metal ions for the subsequent deposition of metal NPs by a reduction of the adsorbed metal ions. For example, Sun et al. (X. Sun et al., 2003) used a silane derivative to functionalize the CNT surface with -SO3H group for the deposition of Pt NPs. The deposition of the Pt NPs was carried out by immersing the CNTs in a solution containing PtCl2, a silane derivative and water in ethanol (X. Sun et al., 2003), which produced a Pt2+ adsorbed CNTs. The CNT supported Pt NPs were formed in a flow of H2 and Ar. Fig. 1 shows the transmission electron microscopy (TEM) images of Pt NPs deposited on CNTs in the absence and the presence of the silane precursor. It shows that the functionalization with silane derivative could facilitate the uniform deposition of Pt on the CNT’s surface, producing well dispersed Pt particles with a smaller size.
A major drawback of the silane-assisted functionalization method is that the electrocatalytic activity of the obtained metal/CNTs catalysts is improved not as largely as it is expected. In this method, an electrochemical insulating layer, organosilane, is inserted between metal and CNTs and thus decrease the interactions between them, which is unforvable for the improvement of the activity of the obtained catalysts. As reported by Ma et al. (Ma et al., 2006), Pt NPs deposited on a silane modified CNTs showed only slightly better electrocatalytic activity in the PEMFC than the commercial electrodes.
Figure 1.
TEM images of Pt NPs deposited on CNTs (a) in the absence and (b) in the presence of the silane precursor. Reprinted with permission from X. Sun et al., 2003. Copyright 2003 Elsevier Science Ltd.
2.1.5. Ionic liquids treatment
Ionic liquids (ILs) represent a group of solvents that consist only of ions existing in the liquid state at low temperatures. Due to their high thermal and chemical stability, high ionic conductivity, wide electrochemical windows, and negligible vapor pressure, ILs are expected to be superior solvents for many chemical processes (Parvulescu & Hardacre, 2007; Welton, 1999) and therefore attract considerable technological and scientific interests in recent years. Advanced progress in the development of catalysts for the PEMFCs applications indicates that an introduction of ILs into the reaction systems for preparing Pt/CNT composites provides a possible way to obtain composites with excellent catalytic and electrocatalytic performance (Park et al., 2009; B.H. Wu et al., 2009).
Figure 2.
Schematic of the modification of CNTs with PIL and the preparation of Pt/PIL-CNTs nanohybrids. EG: ethylene glycol, AIBN: 2,2’-azobisisobutyronitrile.
In an IL based method for the CNT surface functionalization, the CNTs are usually functionalized first to produce a suitable surface for the grafting of the IL molecules. As reported by Zhao et al. (Z.W. Zhao et al., 2006), MWCNTs used for the surface modification were pretreated in concentrated HNO3 before functionalized with ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide. It was reported that the functionalization with the ILs made a big contribution to the formation of small, homogeneous Pt NPs and to the suppression of agglomeration of CNTs. The deposited Pt NPs exhibited an electrochemical surface area with 21% higher than the commercial Pt/C. For the better deposition of metal NPs, Wu et al. (B.H. Wu et al., 2009) reported a novel method based on the thermal-initiation free radical polymerization of the IL monomer, 3-ethyl-1-vinylimidazolium tetrafluoroborate ([VEIM]BF4), to form an ionic-liquid polymer (PIL) on the CNT surface, which introduced a large number of surface functional groups on the CNTs with uniform distribution to anchor and grow metal NPs (Fig. 2). The process of modification by PIL would lead to less structural damage to CNTs than the typical acid-oxidation treatment because of the mild polymerization of the IL monomer. The subsequently deposited Pt and PtRu NPs therefore exhibited a smaller particle size, a better dispersion, a higher electrochemical active area and correspondingly better performance in the direct electrooxidation of methanol than those on the CNTs without the PIL modification.
The disadvantage of the IL based functionalized method is that this approach requires an initial step of the CNT functionalization for the subsequent IL or PIL functionalization. It does not only increase the complexity of process, but possibly causes a structural damage to CNTs although it is alleviated compared to oxidative treatment techniques.
2.1.6. Electrochemical modification
The surface modification of CNTs by an electrochemical method is an attractive approach for functionalization of CNTs. In comparison to other functionalization methods, the electrochemical modification of CNTs can produce CNTs with a C-C covalent bond, which is strong and suitable as a substrate for the deposition of NPs, provides a uniform functional surface, which can effectively prevent the undesired nucleation processes on the CNTs surface, and facilitate the formation of metal NPs with a narrower size distribution due to the specific electrostatic interaction between the substrate and the adsorbed metals. The surface functionalization of CNTs by an electrochemical coupling of aromatic diazonium salts and phenyl residues have been reported (Bahr et al., 2001; Balasubramanian et al., 2003). For example, Guo and co-workers (Guo & H.-L. Li, 2004) covalently functionalized CNTs by grafting an ordered 4-aminobenzene monolayer onto the CNT surface via electro-reduction of 4-nitrobenzenediazonium tetrafluoroborate through cyclic voltammetry (CV), as shown in Fig. 3.
Figure 3.
Schematic for the electrochemical modification of CNTs.
The electrocatalytic properties of Pt/MWCNT composites for methanol oxidation have been investigated by the CV and the high electrocatalytic activity was observed. This might be attributed to the small particle size, high dispersion of platinum particles and the particular properties of the MWCNT supports.
The wrapping of CNTs by polymer molecules was developed by Connel and co-workers (Connel et al., 2001) to prepare individual, well dispersed CNTs in aqueous solution based on the non-covalent attachment of macromolecules on CNTs. The method relies on the thermodynamic favorability of the interactions of CNT–polymer with respect to that of CNT–water, which leads to the hiding of the hydrophobic surface of the CNTs by the attachment of the polymer molecules. When mixing with polyelectrolytes, the energy balance favors CNT wrapping, yielding a high density of charged surface sites which can then serve as a good starting point for the alternating monolayer adsorption of the oppositely charged components through a layer by layer (LBL) technique, driven by electrostatic and van der Waals interactions (Correa-Duarte et al., 2006; Ostrander et al., 2001). As schematically shown in Fig. 4, upon the wrapping of CNTs with a negatively charged polyelectrolyte, a positively charged monolayer can then be deposited, which serves as the real template for the NP adsorption via the electrostatic interactions.
Figure 4.
Schematic illustration of a non-covalent functionalization of CNTs, involving (1) polymer wrapping, (2) self-assembly of polyelectrolytes and (3) NP deposition. Reprinted with permission from Correa-Duarte & Liz-Marzán, 2006. Copyright 2006 Royal Society of Chemistry.
Polybenzimidazole (PBI) (Chemical structure of PBI, Fig. 5a) and its derivatives are some of the most promising candidates for high temperature polymer electrolytes since the proton transfer occurs not only by the vehicle mechanism but also by the hopping mechanism (Q. Li et al., 2004; J.T. Wang et al., 2004), which is an good feature for increasing the rate of the proton transfer and shows great promises in improving the performance of PEMFCs (Okamoto et al., 2008). From the point of view of materials science, PBI can act as a proton-conducting material for PEMFCs that can be operative even under dry conditions above 100 °C (the PEMFC operations at higher temperatures afford many benefits such as decreased carbon monoxide poisoning of the catalyst metal NPs, increased catalytic reaction rate, easy removal of generated water, and so on (Q. Li et al., 2003), and therefore is a promising candidate as a substitution for Nafion, which is a widely used proton exchange membrane (PEM) in low-temperature PEMFC systems (Deluca et al., 2006; Heitner-Wirguin, 1996; Kerres, 2001). Especially, PBI is expected to act as i) a metal adsorbing material via the coordination of the metal ion with the aromatic nitrogen on PBI, ii) a MWCNT-solubilizing material, and iii) a proton conductor. Therefore, studies on the applications of PBI in PEMFCs are of great interests. Indeed, it has already reported that the aromatic compounds have a great potential to individually dissolve SWCNTs through a physical adsorption mechanism based on the π–π interactions (Okamoto et al., 2008). A MWCNT/PBI/Pt nanocomposite has been developed by Okamoto et al. (Okamoto et al., 2009). They reported that as a result of the PBI wrapping, the loading efficiency of the Pt NPs onto the MWCNTs was dramatically improved up to 58.8% compared to that of the pristine MWCNTs (41.0%). The process also allows homogeneous immobilization of Pt NPs onto the surface of MWCNTs. Far-Fourier transform infrared spectroscopy shows the existence of a peak from the Pt–N bonding, indicating that these improvements were derived from the coordination of the Pt ion with the PBI molecules. The CV measurements revealed that the Pt NPs deposited on the MWCNT/PBI showed higher utilization efficiency (74%) as electrocatalysts in the PEMFC application compared to those on the pristine MWCNT (39%).
Figure 5.
Chemical structures of (a) PBI and (b) PyPBI.
A PBI derivative (pyridine-containing polybenzimidazole (PyPBI))-wrapped MWCNTs (PyPBI/MWCNTs) was fabricated by Fujigaya et al. (Fujigaya et al., 2009). Among various types of PBI derivatives reported to date, the pyridine-containing polybenzimidazoles (PyPBI, Fig. 5b) is known to possess significantly higher proton conductivity due to its higher acid doping ability and better mechanical properties compared to the conventional PBIs, which endow them with higher capability of proton transfer and improved stability under the electrochemical process, and therefore is expected to exhibit improved properties in the applications of PEMFCs. The Pt ion can be efficiently adsorbed onto the obtained PyPBI-wrapped MWCNTs via the coordination reaction, and the successive reduction of the Pt ion forms rather uniform Pt NPs on the surfaces of the MWCNT/PyPBI. The CV measurements for the hybrids (MWCNT/PyPBI/Pt) showed a high electrochemical surface area (Fujigaya et al., 2009), which was due to the formation of the ”ideal triple-phase boundary nanostructure“ that was demonstrated by the high resolution TEM (HRTEM) observations as shown in Fig. 6. This result provides useful information for the design and fabrication of highly efficient CNT-based electrocatalysts for the PEFC systems.
Figure 6.
Typical HRTEM image of the MWCNT/PyPBI/Pt. The Pt NPs are penetrated into the thin PyPBI-coating layer to contact closely with the MWCNT surfaces. Reprinted with permission from Fujigaya et al., 2009. Copyright 2009 Elsevier Science Ltd.
Figure 7.
Schematic representation of SDS-MWCNT micelles. Reprinted with permission from J.F. Lin et al., 2010. Copyright 2010 Elsevier Science Ltd.
Surfactants are a class of amphiphilic organic compounds, which contain both hydrophobic groups (their tails) and hydrophilic groups (their heads). Therefore, it is possible to functionalize CNTs with surfactant molecules by non-covalent adsorption of hydrophobic groups onto the surface of CNTs and extension of hydrophilic groups to the adsorption of metal ions and/or metal NPs. The adsorption of surfactants enables homogenous suspension of CNTs as individual tubes by decreasing the interfacial surface tension (Moore et al., 2003). As reported by Richard et al. (Richard et al., 2003) and Islam et al. (Islam et al., 2003), the SDS molecules could be chemically adsorbed on the surface of CNTs with the formation of hemimicelles along the graphite network of CNTs. As shown in Fig. 7 for the schematic structure of SDS-MWCNTs, the hydrophobic tails of the micelles enable attachment to the inert surface of MWCNTs and the hydrophilic heads with negative charge enable separation/dispersion of MWCNTs into individual tubes. Lin et al. (J.F. Lin et al., 2010a) used micelle-encapsulated MWCNTs with SDS as a catalyst support to deposit Pt NPs. The HRTEM images revealed the crystalline nature of Pt NPs with a diameter of ~4 nm on the surface of MWCNTs. A single PEMFC with total catalyst loading of 0.2 mg Pt cm−2 (anode 0.1 and cathode 0.1mg Pt cm−2, respectively) has been evaluated at 80 ◦C with H2 and O2 gases using Nafion-212 electrolyte. The Pt/MWCNTs synthesized by using modified SDS-MWCNTs showed a peak power density of 950 mW cm−2. Accelerated durability evaluation was carried out by conducting 1500 potential cycles between 0.1 and 1.2 V with 50 mV s−1 scan rate, H2/N2 at 80 ◦C. The PEMFC with Pt/SDS-MWCNTs as catalysts showed superior stability in performance compared to the commercial Pt/C composites.
Another promising and intriguing area of developing science is the surface modification of CNTs by the proton-conducting polymers owing to their novel applications in electronic and electro-optical devices. Innovative attempts have been developed to design and synthesize conducting polymer/CNT composite materials for various target applications such as electrochemical devices, light-emitting diodes, chromatography, electrostatic discharge protection, corrosion protecting paint and electrocatalysts. As reported by Selvaraj et al. (Selvaraj & Alagar, 2008), the combination of conducting polymers with CNTs would offer an attractive composite support for electrocatalysts in ethylene glycol (EG) oxidation to enhance the activity and stability based on the morphological modification or electronic interaction between the two components. In that work, polythiophene (PTh) was chosen as the conducting polymer matrix due to its relatively wide potential stability, reproducible synthesis and good electronic conducting properties. The prepared PTh/CNT composites were further decorated with Pt and PtRu NPs by the chemical reduction of the corresponding metal salts using HCHO as the reducing agent. The presence of CNTs in conjugation with a conducting polymer produced a good supports for the catalyst deposition, which allowed the formation of Pt and PtRu NPs with higher dispersion and thereby a better catalytic behavior towards EG oxidation. Results showed that the Pt/PTh–CNT and PtRu/PTh–CNT modified electrodes show enhanced electrocatalytic activity and stability towards the electro-oxidation of EG than the Pt/PTh electrodes.
Treatment of CNTs with surfactants, polymers and other capping agents, are generally tedious and in most cases, additional heat treatment steps are needed to get rid of the non-conducting polymer and surfactants attached to the Pt or Pt alloy NPs. In this respect, Wang et al. (D. Wang et al., 2010) reported a simple and novel method to functionalize the MWCNTs by using tetrahydrofuran (THF) solvent. To demonstrate the effectiveness of the method, they selected the syntheses of Pt and binary PtSn NPs on THF-functionalized MWCNTs due to their importance for the electrooxidation reactions of methanol and ethanol in low temperature fuel cells. THF is an oxygen-containing heterocycle with five-membered rings. The presence of a σ–π attractive force between the π bonds of CNTs and the σ bonds of cyclopentanes of THF enabled the surface functionalization of CNTs due to a π–π stacking (D.Q. Yang et al., 2005a). Such interaction also makes the MWCNTs easily dispersible. The electronegativity difference between carbon and oxygen makes the C–O bond moderately polar with a sterically accessible oxygen atom. In a chloroplantic acid solution, THF adsorbed CNTs could be protonated, which makes the adsorption of PtCl62− and Sn4+ ions to the sterically accessible oxygen atoms by an electrostatic self-assembly. The formation of Pt and PtSn NPs on the MWCNTs could be realized by a H2 treatment as shown in Fig. 8. The TEM image showed that the well-dispersed Pt and PtSn NPs can be directly deposited onto the THF-functionalized MWCNTs without any prior chemical oxidation treatments and the as-prepared Pt/MWCNT and PtSn/MWCNT catalysts show a high activity and stability for the ethanol oxidation in acid solutions. The advantages of the THF-functionalized CNT catalyst support are its simplicity and effectiveness in the deposition of highly dispersed Pt and Pt alloys on CNTs.
Figure 8.
Schematic of the synthesis of PtSn NP catalysts on the THF-functionalized MWCNTs. Reprinted with permission from D. Wang et al., 2010. Copyright 2010 Elsevier Science Ltd.
2.3. Plasma surface modification
The surface modification and functionalization methods described above, such as the addition of polyelectrolytes, supramolecular complexation with surfactants, functional organics, or polymers, could effectively increase the surface binding sites on the surface of CNTs for the subsequent deposition of metal NPs, avoid the aggregation of metal NPs, improve the dispersion of metal NPs, and simultaneously reduce the average size of metal NPs deposited (R.J. Chen et al., 2001, 2003; Holzinger et al., 2001; Star et al., 2001). In most cases, however, some severe problems accompanied with such surface modification and functionalization methods, such as uneven distribution of the surface functional groups, structural damage, blockage of the direct touch between metal NPs and MWCNTs, could lead to partial lose in the electrical conductivity of the carbon supports, reduce the interactions between metal and CNTs, and thereby the performance of the obtained electrocatalysts (Anderson et al., 2002; Hsin et al., 2007). Additionally, these methods usually require the use of a large amount of chemicals, toxic solvents and/or extreme conditions, which is easier to cause environmental pollution. In order to minimize the above disadvantages during the preparation, it is highly desired to develop a mild surface functionalization technique to introduce homogeneous distributed functional groups with a high density onto the surface of CNTs, but cause less structural damage to the CNTs (and thus retain good electrical conductivity) and no pollution to the environment. Various dry processes, including both nonreactive and reactive plasmas (Brunetti et al., 2008; Q. Chen et al., 2000, 2001; Khare et al., 2004; Plank et al., 2003, 2004; Yan et al., 2005) and low-energy ion beam bombardment in a vacuum (D.Q. Yang et al., 2005), have been found as good candidates. Compared to wet approaches, dry plasma processing may be easier to control, with relatively less contamination. Plasma treatment is an efficient method in the field of surface modifications. The excited species, radicals, electrons, ions, and UV light within plasma strongly interact with the surfaces of CNTs breaking the C=C bonds and creating active sites for binding of functional groups, as a result, chemical and physical modifications occur on the surfaces. Compared to other chemical modification methods, the plasma treatment method has the advantages of shorter reaction time, nonpollution, and providing a wide range of different functional groups depending on plasma parameters such as power, used gases, treatment time, and pressure. Thus, this method offers the possibility of scaling up to produce large quantities necessary for commercial use. Plank et al. (Plank et al., 2003) reported the surface functionalization of CNTs by CF4 plasma. The reaction was conducted at the room temperature in a short duration of time. Scanning electron microscopy (SEM) images indicates the dimension and morphology of CNTs have been preserved after a CF4 plasma exposure. X-ray photoelectron spectroscopy (XPS) demonstrates the prevalence of covalent C–F bonds on the CNTs after CF4 exposure. Recently, Yang et al. (D.Q. Yang & Sacher, 2006; G.X. Zhang et al., 2007) studied the effect of plasmas on highly oriented pyrolytic graphite (HOPG), where they found that Ar, O2, N2, and H2O plasmas could break C-C bonds, producing -C free radical defects that, on atmospheric exposure, reacted with components of air (H2O and O2) to produce oxidized carbon species (C-OH, C=O, and COOH). These oxidized carbon species could facilitate the deposition of metal NPs due to hydrogen bonding between the hydroxyl groups on the NP surface and these species on the HOPG that are introduced upon atmospheric exposure of the free radicals produced during the plasma treatment. Similar results were reported to a plasma modification of CNTs (D.Q. Yang & Sacher, 2008). It showed that the exposure of CNTs to Ar plasma or O2 plasma produced surface defects on the surface of CNTs which could act as both nucleation and binding sites for the deposition of Pt NPs. The XPS and TEM analyses showed that the interactions between Pt NPs and CNTs were enhanced by the Ar or O2 plasma treatment.
The possible mechanisms associated with the plasma treatment of CNTs include the generation of the C-O, C=O, and O-C=O bonds, as shown in Fig. 9 (C. Chen et al., 2009). Since the π bonds in C=C are active and are the most susceptible to the plasma attacks, it is believed that the radicals are first generated on the dissociated π bonds in C=C, which further react with active oxygen atoms (Fig. 9A). This explains the decrease in the C=C fraction after a plasma treatment. This process may produce C-O bonds, and then the C-OH bonds are formed through stabilization by hydrogen atom transfer from the same or a neighboring chain. The hydrogen atoms can also be introduced during the synthesis phase of MWCNTs or via atmosphere exposure. Oxygen radicals are considered to be generated on the surfaces of MWCNTs, which could lead to the formation of the new C=O bonds through intramolecular reorganization on the C-C bonds, as shown in Fig. 9B. The formation of O-C=O bonds is believed to be due to the C=O bonds through the combination of the plasma-generated radicals on the C=O bonds with the active oxygen atoms. After stabilization with proton transfer, HO-C=O can be formed, as shown in Fig. 9C. Compared to pure O2 plasma treatment, Ar/O2 plasma treatment enhances the C-O and O-C=O fractions, and the C-O and O-C=O fractions increase with increasing plasma power and the treatment time. The efficiency of Ar/O2 mixture gas plasma treatment is higher than that of pure O2 plasma treatment, since the content of active oxygen in Ar/O2 mixture gas plasma is higher than that in pure O2 plasma. Ar atoms and/or ions present in the plasma can also interact with the surfaces of MWCNTs creating active sites for further oxygen functionalization. Indeed, in some case, N-containing groups can also be formed on the surface of CNTs (Ruelle et al., 2008 and C. Chen et al., 2010). A plasma discharge can create enough electron energy to fractionize NH3, forming metastable ions of NH2, NH, N, and H as well as radicals, which can be incorporated into the surface of CNTs during the plasma treament.
Figure 9.
Possible mechanism of MWCNT oxidation by Ar/O2 mixture gas plasma treatment: (A) generation of C-O bonds; (B) generation of C=O bonds; (C) generation of O-C=O bonds; (D) transfer between carboxyl and lactone. Reprinted with permission from C. Chen et al., 2009. Copyright 2009 American Chemical Society.
The investigation of the electrocatalytic activity of Pt NPs on the plasma treated CNTs has been conducted by our group (Jiang et al., 2009, 2011). The results showed that the Pt NPs on the N2 plasma treated CNTs exhibited a significantly higher electrochemical activity towards the methanol oxidation in an acid solution, in comparison to those on the CNTs functionalized by other modification methods. The structures of CNTs and the catalyst/CNTs interactions were found to play important roles in determining the performance of the catalysts. The Pt NPs deposited on the MWCNTs functionalized by a strong acid treatment which easily leads to the structural damage of MWCNTs showed a much lower performance of Pt/MWCNTs in methanol oxidation reaction, due to the decrease in the conductivity of MWCNTs caused by the structural damage. An insertion of impurities between Pt NPs and MWCNTs could also result in a decrease in electron migration from metal to MWCNTs and give rise to the decrease of electrochemical performance of Pt/MWCNTs in methanol oxidation reaction. It therefore suggests that to obtain Pt/MWCNTs with higher catalytic activities, it is necessary to adopt a mild surface modification approach and to make metal NPs directly deposit onto the CNT surface.
2.4. Nitrogen-doped CNTs
As mentioned above, a chemical modification of the surface of CNTs by covalent functionalization could reduce considerably the mechanical and electronic performance of CNTs due to the introduction of large numbers of defects, and in some cases, the electrocatalysts on the non-covalently functionalized CNTs shows low activity over fuel oxidation due to the poor conductivity of functional molecules and low conduction between the metal NPs and the CNTs and between the neighboring CNTs, which require us to seek for new approaches for the preparation of electrocatalysts. It is recently found that the use of nitrogen doped CNTs (N-CNTs) could be considered as one of promising options. The introduction of N can lead to the formation of CNTs with high surface areas (Feng et al., 2008), high densities of defects (Tao et al., 2007), chemically active impurity sites (Nxumalo et al., 2008; Tao et al., 2007) and narrow widths (the numbers of walls decrease with N inclusion) (Nxumalo et al., 2008). The N-doped nanotubes are found to be either metallic or narrow energy gap semiconductors (Huang et al., 2000; Miyamoto et al., 1997), thus offering the possibility of greater electrical conductivity as compared to the pure CNTs. Studies have shown that the N-doped CNTs and their composites can be used as support materials and have great potentiality in the PEMFC catalyst applications. Due to the presence of chemically active nitrogenated sites (substitutional and pyridinic nitrogen), the N-doped CNTs are reported to have enhanced activity and selectivity in many catalytic applications (Shao et al., 2008), and exhibit a strong binding to metals, leading to excellent metal dispersion in the metal/N-CNT materials (Droppa Jr. et al., 2002). It can therefore avoid using functionalization processes that might be detrimental to the catalytic properties of the obtained metal/N-CNT composites (Maiyalagan et al., 2005; C.L. Sun et al., 2005; C.-H. Wang et al., 2006, 2007; Zamudio et al., 2006). For example, Maiyalagan et al. (Maiyalagan et al., 2005) studied the electrocatalytic properties of Pt/N-CNTs synthesized by a reduction of Pt2+ adsorbed on the surface of unfunctionalized N-CNTs. The obtained N-CNT-supported Pt NPs were reported to be homogeneously dispersed on the nanotubes. An enhanced catalytic activity and stability toward methanol oxidation was observed with Pt/N-CNTs in comparison with commercial Pt/C catalyst supplied by E-TEK. The authors of that work attributed the enhanced catalytic activity and stability of Pt/N-CNTs to the factors, such as, the higher dispersion of Pt NPs which increased the availability of electrochemically active surface area, the appearance of the specific active sites at the metal–support boundary and strong and specific metal–support interaction. The investigation of the microstructure and electrochemical activity of the PtRu supported by N-CNTs was reported by Wang et al. (C.-H. Wang et al., 2006). These N-CNTs were directly grown on the carbon cloth (N-CNTs–carbon cloth composite electrode) using a microwave plasma enhanced chemical vapour deposition, and then used as the template to support the subsequently sputtered PtRu nanoclusters. The ferricyanide/ferrocyanide redox reaction in CV measurements showed a faster electron transfer on the N-CNTs–carbon cloth composite electrode than the one with carbon cloth alone. In addition, it was found that the PtRu nanoclusters supported by the N-CNTs–carbon cloth composite electrode had considerably higher electrocatalytic activity in the methanol oxidation than the carbon cloth counterpart, which suggested a high performance of the N-CNTs/carbon cloth composite electrode, its suitability for direct methanol fuel cell applications.
3. Synthesis and characterization of metal NPs supported on CNTs
It is know that the electrocatalytic activities of catalysts on the CNTs are greatly dependent upon their size, morphology, composition and dispersion, which are determined by the way that they are produced and the way they are adsorbed onto the surface of CNTs. Since the dispersion and particle size of metal NPs largely determine the utilization and catalytic activity of metal/CNTs, the synthesis of metal NPs supported by CNTs with a controlled manner is of great importance for the design of catalysts of higher efficiency. Up to now, the most widely used catalysts for the application of PEMFCs are Pt and Pt-based alloys due to their large surface to volume ratio, improved catalytic activities relative to their bulk material. The synthesis of metal NPs/CNT composites can be performed either by nucleation and growth of metal NPs on the surface of CNTs or by attachment of preformed NPs in the bulk solution onto the surface of CNTs. In the following sections, the methods used to prepare NPs/CNTs will be reviewed and discussed.
3.1. Formation of metal NPs directly on CNTs
Nucleation and growth of metal NPs directly on the surface of CNTs is the mostly used method to prepare metal NPs/CNTs catalysts. The preparation of such NPs/CNT composites can be conducted either physically or chemically. Metal NPs are absorbed on the surface of MWCNTs mainly based on van der Waals interactions, electrostatic interactions and coordination interactions between metal particles and functional groups, which in some cases seem to be sufficiently strong to guarantee meaningful adhesion (K.C. Lee et al., 2006; X. Sun & Saha, 2008).
3.1.1. Physical methods
In a physical method, bulk metals are thermally vaporized followed by a sputtering of metal gases onto the surface of CNTs. The sputtering-deposition method is a recently developed approach to prepare the PEMFC cathode catalysts, aiming at metal loading reduction and metal utilization improvement. It has been demonstrated that the sputter-deposition technique is a good way to deposit small and uniform metal NPs on CNTs with sizes well controlled by the sputtering time and current. This method can also generate a thinner catalyst layer that could give a higher fuel cell cathode performance and, at the same time, considerably reduce the metal loading. The physical deposition of Pt NPs on the surface of CNTs was reported by Tang et al. (Z. Tang et al., 2010), who produced Pt NPs with 4 nm in diameter and a narrow size distribution. A high maximum power density of 595 mW cm−2 was observed for a low Pt loading of 0.04 mg cm−2 at the cathode for the PEMFC application. The deposition of Pt NPs on nitrogen-dopped MWCNTs (N-MWCNTs) was done by Sun et al. (C.L. Sun et al., 2005). The well-separated Pt NPs with an average diameter of 2 nm were formed on the side-walls of N-MWCNTs. In that work, the nitrogen incorporation in the MWCNTs might play a critical role in the self-limited growth of the Pt NPs. The CV results showed that the Pt/N-MWCNT catalyst had improved electrochemical activity towards methanol oxidation and showed great promises for a future µDMFC device. However, because the preparation of Pt/CNT composites usually requires the use of extremely high temperatures, this technique may face some technical challenges with respect to the electrode mass production.
3.1.2. Chemical methods
Compared with the physical methods, the chemical methods have the significant advantage of being able to easily control the primary structures of NPs, such as size, shape, and composition, as well as to achieve mass production. A large variety of chemical methods such as impregnation method, colloidal method, ion-exchange method, electrochemical method, microwave heated polyol method, have been reported for the preparation of metal/CNTs composites as a catalyst for the DMFC applications. Different growth control mechanisms and strategies are used in each of the different chemical deposition methods.
3.1.2.1. Impregnation method
The impregnation method is the most widely used wet-chemical method, which is a simple and straightforward for depositing metal NPs on the CNTs for the preparation of the PEMFC catalysts and is thus an attractive choice for a large-scale synthesis. The method involves the impregnation of the support material with a salt solution containing the metal to be deposited, followed by a reduction step (Asano et al., 2006; Liao et al., 2006; Y. Lin et al., 2005; Lordi et al., 2001). During an impregnation process, metal ions are initially adsorbed to the surface of functionalized CNTs by homogeneously mixing CNTs with the metal precursors in a solution. The chemical reduction of the metal ions on the surface of the CNTs can either be carried out by a liquid phase reduction using borohydride, formic acid or hydrazine as a reductive agent, or by a gas phase reduction using a flowing hydrogen gas as a reductive agent under elevated temperature. For the impregnation method, the size and distribution of Pt NPs are affected by many factors, in which the chemical modifications of the surface of CNTs will play a major role since the pristine surface of CNTs is relatively inert unfavorable for the deposition of metal NPs. A desired way in this case is to functionalize the surface of CNTs first through a chemical reaction as discussed in Section 2. As one example, Li and coworkers (W.Z. Li et al., 2004) reported the synthesis of Pt/MWCNT nanocomposites by using the impregnation method, which was then used as electrocatalyst applied in a direct methanol fuel cell (DMFC). In that work, the Pt NPs were deposited on the pre-functionalized MWCNTs by reduction of Pt precursor with EG, which produced a Pt/MWCNT composite with a homogeneously dispersed spherical Pt NPs of a narrow particle size distribution. The obtained Pt/MWCNTs were characterized to exhibit significantly higher performance than the Pt loaded on the commercial XC-72 carbon when used in the DMFC. This improvement in catalytic performance was attributed to the greater dispersion of the supported Pt particles.
3.1.2.2. Electrochemical method
The electrochemical method for the preparation of metal/CNTs is very similar to the process of the impregnation method, except for an electrochemical reduction of the adsorbed metal ions rather than the chemical reduction. In this process, functionalized CNTs are first mixed with the metal precursors in aqueous solution to produce a homogeneous solution. A pulse current, such as direct current or CV, is then added for the reduction of metal ions promoting the deposition of metal NPs on CNTs, which usually produces metal NPs/CNTs with high efficiency in PEMFCs as compared to those prepared by the conventional deposition techniques (Choi et al., 1998; Taylor et al., 1992; Thompson et al., 2001). An approach for the electrochemical deposition of Pt particles with a narrow size distribution on CNTs was reported by Tsai et al. (Tsai et al., 2006), who successfully electrodeposited Pt and PtRu NPs on the dense CNTs directly grown on carbon cloths in EG containing H2SO4 aqueous solutions. Prior to the electrodeposition of Pt or PtRu NPs, all the specimens with CNTs directly grown on carbon cloths (CNT/CC) underwent a hydrophilic treatment at 50 mV s–1 for 100 cycles with potential ranged from –0.25 to +1.25 VSCE (VSCE means that the potential was quoted against a saturated calomel electrode (SCE)) in an O2 saturated 2 M H2SO4 aqueous solution at ambient condition. To achieve a larger driving force for dechlorination of the Pt and Ru precursors, more negative deposition potentials are usually favorable. EG acted as a stabilizing surfactant to prevent the particles from agglomeration during the electrodeposition processes and could also enhance the dechlorination of Pt and Ru precursor salts and led to the formation of NPs. In the meantime, nano-sized Pt and PtRu particles were also found in specimens treated at two pre-selected negative potentials. The particle sizes of Pt on CNTs ranging from ~4.5 to ~9.5 nm and PtRu on CNTs (PtRu/CNTs) ranging from ~4.8 to ~5.2 nm were obtained and was reported to exhibit improved electrocatalytic activity in methanol oxidation in comparison to the corresponding commercially available catalysts.
3.1.2.3. Colloidal method
Colloidal method involves the nucleation of metal clusters on the surface of CNTs, followed by growth of these clusters, or involves the formation of a metal oxide colloid, followed by simultaneous reduction and adsorption, or adsorption followed by chemical reduction. In this method, the size of the metal NPs is largely controlled or stabilized by the protecting agents, such as ligands, surfactants or polymers (Kuo et al., 2005). The colloidal metal NPs are stabilized by either steric hindrance or by electrostatic charges. In recent years, there have been considerable interests in the development of colloidal methods to prepare Pt catalysts supported on the CNTs with a narrow particle size distribution (Kongkanand et al., 2006b; C. Lee et al., 2005; W.Z. Li et al., 2003; X. Li et al., 2004, 2006; Yoshitake et al., 2002). For example, Li and co-worker (X. Li et al., 2004) used the surfactant 3-(N,N-dimethyldodecylammonio) propanesulfonate (SB12) as a stabilizer to prepare Pt NPs supported on the CNTs by reduction of H2PtCl6 with methanol (X. Li et al., 2004, 2006). The Pt NPs deposited on the functionalized CNTs were well-dispersed with an average size of 2.2 nm (X. Li et al., 2004).
Though the colloidal method can provide a narrow size distribution of metal NPs, the major drawback is the presence of a protecting agent, which may decrease the catalytic performance of the NPs. As a result, the organic protecting layers used for the protection of the electrocatalysts prepared by the colloid method must be removed prior to their use in the PEMFCs. The desired way is to prepare colloidal NPs without the use of protecting agents. Such fascinating way has been recently reported by Yoshitake et al. (Yoshitake et al., 2002), who synthesized a Pt/CNT catalyst for the use of PEMFCs by the colloid method. In the preparation, a colloidal Pt oxide was first prepared by adding NaHSO3 and H2O2 into an aqueous solution of H2PtCl6 without using an organic stablizer. The adsorption of the Pt oxide colloids was done through its mixing with the single-wall carbon nanohorns (SWNH) powder. The reduction of Pt oxides was carried out by a H2 gas. The produced Pt/SWNH catalyst showed very homogeneous dispersion of Pt NPs with an average size of 2 nm and exhibited higher electrocatalytic activity in a PEMFC.
3.1.2.4. Ion-exchange method
An ion-exchange method is an effective technique for depositing metal NPs on the CNTs without using protecting agents, reducing agents or precursor complexes. In this technique, a metal cation complex, such as [Pt(NH3)4]2+, is ion-exchanged with hydrogen ions of the acid functional groups on the surface of the CNTs. After the ion-exchange process, the Pt cation complex is reduced to the Pt NPs in an H2 atmosphere. The interaction between the acid functional groups and the Pt precursor determines the dispersion and size of the metal particles. The preparation of a Pt/CNT composite by the ion-exchange method has been reported by Yin and co-workers (Y. Shao et al., 2006; J. Wang et al., 2007). In their work, an electrochemically functionalized CNT electrode was immersed in a solution of the platinum cation-complex salt for 48 h, which resulted in the ion-exchange of the hydrogen ions of the functional group on the surface of the CNTs with the Pt cation complex. The immersed CNTs was then filtrated and washed thoroughly with distilled water. The reduction of the adsorbed platinum complex precursor to its metallic form was carried out by the treatment with hydrogen gas at 190 °C. It was reported the Pt NPs were highly dispersed on the CNTs with dispersion much better than those prepared by the borohydride method (J. Wang et al., 2007).
3.1.2.5. Microwave heated polyol method
In a microwave heated polyol method, a polyol (ethylene glycol) solution containing catalyst metal precursor salts is refluxed at high temperature by a microwave heating in order to homogeneously decompose EG and create an active reducing agent for metal ions (W. Chen et al., 2005; Z. Liu et al., 2005). A metal support could be optionally present to capture the depositing metal particles in this process. Unlike the conventional conductive heating strategy used to thermally activate the polyol, which has a heterogeneous temperature distribution, the fast heating by microwaves can accelerate the reduction of the metal precursor ions and the nucleation of the metal NPs. In addition, the homogeneous microwave heating could reduce the temperature and concentration gradients in the reacting sample solution, resulting in a more uniform environment for the nucleation and growth of metal particles (W. Chen et al., 2005; Z. Liu et al., 2005). The synthesis of Pt/CNT or PtRu/CNT catalysts using a microwave heated polylol process (W. Chen et al., 2005; Z. Liu et al., 2004, 2005) has been reported by several research groups. The obtained Pt/CNT or PtRu/CNT catalysts are usually characterized with greater catalytic activity towards oxygen reduction than the catalysts fabricated by some other techniques although both catalysts had almost the same Pt particle sizes.
3.2. Connecting metal NPs and CNTs
In the methods presented above for the preparation of metal/CNT composites, the formation of metal NPs directly occurs on CNTs. However, in some cases, the deposition of metal NPs is realized by adsorption of preformed metal NPs in the solution through either the formation of covalent bonds between the functional groups on metal NPs and the functional groups present on the CNT surface or the intermolecular interactions such as hydrophobic, π–π stacking or electrostatic attractions between them (Georgakilas et al., 2007).
3.2.1. Covalent linkage
The metal NPs anchored on CNTs by a covalent linkage usually exhibit a long life and high catalytic performance when used in PEMFCs. Due to the high strength of the covalent interactions, the metal NPs are usually well separated on the CNTs and exhibit a higher stability during the electrochemical process. The higher degree of dispersity increases electrocatalytically active surface areas of metal NPs which therefore exhibit a high activity in methanol oxidation and oxygen reduction. For example, Yang et al. (D.Q. Yang et al., 2006b) reported the fabrication of Pt/CNTs by the covalent attaching of the Pt NPs onto the CNTs using benzyl mercaptan as an interlinker. In their work, the CNTs were first functionalized with benzyl mercaptan by a π-Stacking. The functionalized CNT surface interacted strongly with the Pt NPs through the formation of Pt-S bonds and resulted in a very high Pt NP loading both high dispersion and a narrow size distribution, as schematically illustrated in Fig. 10.
Figure 10.
Schematic of (a) a CNT functionalized with benzyl mercaptan via π-π bonding and (b) the bonding of Pt NPs to the functionalized CNT via covalent S-Pt bond formation. Reprinted with permission from D.Q. Yang et al., 2006b. Copyright 2006 American Chemical Society.
3.2.2. Hydrophobic interactions and hydrogen bonds
The interactions between hydrophobic ligands forming the monolayer passivating the metal surface with hydrophobic molecules adsorbed on CNTs and hydrogen bonds between the molecules on NPs and CNTs can be used to immobilize the metal NPs onto CNTs. A combination of hydrophobic and hydrogen bond interactions will make the attachment of metal NPs on CNTs more tightly, and therefore be employed as a promising way to the preparation of metal/CNT composites as catalysts for PEMFC applications (L. Han et al., 2004). As reported by Han et al. (L. Han et al., 2004), a Au/CNT composite has been synthesized by the hydrophobic interactions of the alkyl chains on decanethiol and mercaptoundecanoic acid adsorbed Au NPs with the CNT surface and hydrogen bonds between carboxylic groups of CNTs and those present on the NP surface. Due to the strong interactions provided by the hydrophobic interactions and the hydrogen bonds between ligated Au NPs and CNTs, the obtained Au/CNTs showed a very stable structure, cannot be disassembled by sonication in hydrophobic solvents. However, thermal treatment of the sample, for example, at 300 ℃ would induce aggregation of NPs that stick strongly to the nanotube surface due to the removal of the capping shells of the Au NPs, which decreased the interactions between Au NPs and CNTs (Georgakilas et al., 2007).
3.2.3. π-Stacking
The deposition of metal NPs through the π-Stacking involves a cover of metal NPs with phenyl-containing molecule and the adsorption onto the surface of CNTs by a π-Stacking interaction. As recently reported by Mu et al. (Mu et al., 2005), they have applied this method to prepare the Pt/CNTs by the surface modification of Pt NPs with triphenylphosphine (PPh3) and the subsequent deposition of the modified Pt NPs onto the CNTs through the π-Stacking. The main disadvantage of the method is that a special annealing process is usually required to remove PPh3 molecules, which might lead to some degree of aggregation of Pt NPs. Indeed, it is demonstrated that even though the thermal treatment would result in aggregation of Pt NPs, the mean size of the deposited Pt NPs remained small and showed higher electrocatalytic activity and better tolerance to poisoning species in the methanol oxidation than the commercial E-TEK catalyst.
3.2.4. Electrostatic interactions
Electrostatic interaction is a commonly used method to anchor metal colloids to CNTs. Because the functionalized CNTs with an ionic polyelectrolyte are charged, which can serve as an anchor for metal NPs oppositely charged. In typical examples, the oxidized CNTs are modified with a cationic polyelectrolyte and exposed to the negatively charged metal NPs. By choosing different kinds of polyelectrolytes the surface of the CNT can be also negatively charged in order to the deposit of positively charged NPs. The electrostatic approach has been used to build mixed Au/MWCNT layers using the LBL (layer-by-layer) methodology (Kim & Sigmund, 2004). In the work, the acid-functionalized MWCNTs were first covered with a layer of a positively charged polymer [PDDA, poly(diallyldimethylammonium chloride)] and then with a layer of a negatively charged polymer [PSS, poly(sodium 4-styrenesulfonate)]. Subsequently, the positively charged Au NPs were anchored through electrostatic interactions to the PSS layer. The positively charged Au NPs may also interact directly with the MWCNTs presenting carboxylate groups on their surface. However, the direct binding happened with a much lower density of Au deposition than that observed for the PDDA/PSS LBL method.
4. Activity validation of the synthesized catalysts in a fuel cell operation
The most direct and effective method for the activity validation of the synthesized catalysts is to directly use them in a single fuel cell. For fuel cells, the activity of a catalyst can be deduced from their performance. The most commonly used way to reflect the performance of the fuel cells is the polarization (or current-voltage) curve of the MEA which is the core of the PEM fuel cell, composed of an anode gas diffusion layer (GDL), an anode catalyst layer, a membrane (the PEM), a cathode catalyst layer, and a cathode gas diffusion layer, as shown in Fig. 11 which schematically shows a single typical PEMFC. Two data collection modes are frequently used in obtaining the polarization curve, conducted either by adjusting the cell voltage then recording the current density, or by adjusting the current density then recording the cell voltage, with the latter being the most popularly used in the fuel cell performance data collection. A typical polarization curve of a cell obtained by collecting the cell voltage as a function of current density is shown in Fig. 12, which can then used to yield the power density of the MEA (cell voltage × current density) plotted as a function of current density. From the power density curve, the maximum power density of the fuel cell MEA can be then known as well as the maximum volume power density and the mass power density of a fuel cell stack. In principal, beside the catalysts, the performance of a fuel cell (polarization curve) is also affected by the quality and property of MEA and the operating conditions, such as temperature, pressure, relative humidity (RH), gas flow rates, etc. Therefore, for the sake of systematical improvements in the efficiency of the fuel cell, a better understanding of the effects of the quality and property of the MEA on the performance of the fuel cell is essential.
Figure 11.
Schematic of a single typical PEMFC.
Figure 12.
Typical polarization curve of PEMFCs.
4.1. Synthesis of metal/CNT based MEA
As the core of the PEM fuel cell, the MEA conducts the conversion of the chemical energy of the fuel (i.e., hydrogen) into electricity through the electrochemical oxidation of fuel at the anode and the electrochemical reduction of oxygen at the cathode. Therefore, the MEA component materials, structure, and fabrication technologies largely determine the performance of a PEMFC. An optimization of MEA is of great importance for the improvement of the PEMFC performance (Shen, 2008). An ideal MEA allows all active sites of catalysts in the catalyst layer to be accessible to the reactant, protons and electrons, and can effectively remove produced water from the catalyst layer (CL) and gas diffusion layers (GDL). As mentioned above, a typical MEA for a single PEMFC (J.M. Tang et al., 2007), is composed of a PEM, anode and cathode electrodes, and anode and cathode GDL (schematically shown in Fig. 11). According to differences in preparation processes and structures, hydrophilic catalyst layers can be prepared either by a membrane-based or a GDL-based method, as shown in Fig. 13. For the membrane-based method, the MEA is fabricated by depositing the catalyst ink directly onto a dry and fixed membrane or by coating catalyst ink onto a blank substrate (e.g., PTFE film) and then transferring the coating catalyst ink onto the membrane (Wilson & Gottesfeld, 1992), which is then sandwiched between two GDLs and followed by a hot pressing step, while in the GDL based method, the catalyst ink is directly painted or sprayed onto the pre-treated GDL and then hot pressed onto the membrane. In these two methods, the catalyst ink used for coating the membrane and a blank substrate and the GDLs can be prepared by mixing the metal/CNT catalyst with ionomer firstly, which can improve the contact between the catalyst particles and the ionomer, and thus help to improve catalyst utilization. It has been reported that an ionomer-bonded hydrophilic catalyst layer could improve Pt utilization by up to 45.4% (Cheng et al., 1999). The notable advantages of such an ionomer-bonded hydrophilic electrode include (Girishkumar et al., 2005):
improved bonding between the membrane and the catalyst layer;
uniform continuity of the electronic and ionic paths for all catalyst sites due to the uniform dispersion of catalyst in the ionomer;
high metal NPs utilization resulting from good contact between the catalyst and the protonic conductor;
relatively low catalyst loading without performance losses.
However, there are still some inevitable drawbacks associated with this kind of catalyst layers. For example, due to the lack of hydrophobic passages, gas transportation from the GDL to the reaction sites becomes difficult, and the produced water tends to accumulate in the electrode and block the gas transport paths, leading to a decrease in fuel cell performance. In addition, due to the degradation of the ionomers, its ability to bind with the catalyst particles will decrease, causing lowered reliability as well as durability problems. Recent efforts, therefore, turn to the preparation of the catalyst layers with reduced thicknesses. A thin catalyst layer can minimize the shortcomings associated with an ionomer-bonded hydrophilic catalyst of thick layer and improve the efficiency of the mass transfer at the interface, such as the efficient movement of protons, electrons, and dissolved reactants in the reaction zone, which is beneficial to reduce catalyst loading and increase mass power density of a MEA. However, this requires the use of catalysts of higher efficiency.
Figure 13.
Configuration of MEAs for (a) the CL on GDL mode and (b) the CL on membrane mode. GDL – gas diffusion layer; CL – catalyst layer; M – membrane.
Good dispersion of metal NPs. The well-dispersed NPs on the surface of CNTs make them more accessible to the fuel oxidation reaction.
Unique structure of CNTs. Because of the novel morphology and electrical properties of CNTs, a fast transfer of charges through the composites is possible, which results in their high electrocatalytic activity.
Small sizes of deposited metal NPs. The surface-to-volume ratio becomes larger when the size of NPs decreases, which increases the percentage of atoms at the surface accessible to the fuel oxidation reaction. In addition, with decreasing the size of metal NPs, their Fermi level improves, which make the electron transfer easier, favoring the subsequent redox reaction.
High purification of CNTs. The metal NPs are reported to be sensitive to some elements, such as sulfur. Trace amount of sulfur adsorption would lead to a decrease in the catalytic activity of metal NPs. The CNT supports contain fewer organic impurities, unlike other carbon materials such as the XC-72 carbon (contain ca. 0.2 at. % sulfur), which is important to maintain the high catalytic activity of metal/CNTs.
Porous structures of CNTs. Porous structures influence the reactant-product mass transport and therefore have a big effect on the activities of catalysts.
5. Conclusions and outlooks
In the PEMFCs, the conversion of chemical energy of the fuel (i.e., hydrogen) into electricity is carried out by the catalysts, which is of great importance in determining the performance of the PEMFCs. Many years of studies give strong evidences that metal/CNTs are more active in the fuel catalytic oxidation and provide better performance than other catalyst systems when used in the PEMFCs and thus attract tremendous attentions in recent years. However, for the preparation of metal/CNTs, surface functionalization of the CNTs is mostly required to produce the CNTs with suitable surface properties for metal deposition. The surface functionalization might lead to the structural destruction of the CNTs, which is detrimental to prepare the metal/CNTs of high efficiency in catalysis. It is generally believed that a mild surface modification method is desired for the functionalization of CNTs, which can effectively prevent the CNTs from the structural destruction and has great promises to synthesize the high efficient metal/CNT catalysts. Additionally, besides the functionalization methods, the catalytic activity of the metal/CNTs is also affected by the size and dispersion of the deposited metal NPs. For rational design of catalysts of high efficiency, it is therefore essentially important to know exactly the factors that affect the activity of the catalysts.
Currently, although the development of PEMFCs is moving toward commercialization due to the impressive research effort in recent years, significant challenges including detailed mechanism how the CNTs affect the catalytic activity of the metal/CNTs and high materials cost remain to be solved. It is clear that this research in these areas would be one of important on-going topics in the development of more highly efficient catalysts with low cost to meet the requirements of fuel cell commercialization.
\n',keywords:null,chapterPDFUrl:"https://cdn.intechopen.com/pdfs/17086.pdf",chapterXML:"https://mts.intechopen.com/source/xml/17086.xml",downloadPdfUrl:"/chapter/pdf-download/17086",previewPdfUrl:"/chapter/pdf-preview/17086",totalDownloads:3890,totalViews:416,totalCrossrefCites:2,totalDimensionsCites:4,hasAltmetrics:1,dateSubmitted:"October 13th 2010",dateReviewed:"April 11th 2011",datePrePublished:null,datePublished:"August 9th 2011",dateFinished:null,readingETA:"0",abstract:null,reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/17086",risUrl:"/chapter/ris/17086",book:{slug:"carbon-nanotubes-growth-and-applications"},signatures:"Zhongqing Jiang and Zhong-Jie Jiang",authors:[{id:"25603",title:"Dr.",name:"Zhongqing",middleName:null,surname:"Jiang",fullName:"Zhongqing Jiang",slug:"zhongqing-jiang",email:"zhongqingjiang@hotmail.com",position:null,institution:{name:"Ningbo University of Technology",institutionURL:null,country:{name:"China"}}},{id:"37285",title:"Dr.",name:"Zhong-Jie",middleName:null,surname:"Jiang",fullName:"Zhong-Jie Jiang",slug:"zhong-jie-jiang",email:"zhongjiejiang1978@hotmail.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction ",level:"1"},{id:"sec_2",title:"2. Methods for functionalization of CNTs",level:"1"},{id:"sec_2_2",title:"2.1. Covalent functionalization",level:"2"},{id:"sec_2_3",title:"2.1.1. Oxidative treatment of CNT surfaces",level:"3"},{id:"sec_3_3",title:"2.1.2. Photochemical oxidation of CNT surfaces",level:"3"},{id:"sec_4_3",title:"2.1.3. Sonochemical treatment",level:"3"},{id:"sec_5_3",title:"2.1.4. Silane-assisted method",level:"3"},{id:"sec_6_3",title:"2.1.5. Ionic liquids treatment",level:"3"},{id:"sec_7_3",title:"2.1.6. Electrochemical modification",level:"3"},{id:"sec_9_2",title:"2.2. Non-covalent functionalization",level:"2"},{id:"sec_10_2",title:"2.3. Plasma surface modification",level:"2"},{id:"sec_11_2",title:"2.4. Nitrogen-doped CNTs ",level:"2"},{id:"sec_13",title:"3. Synthesis and characterization of metal NPs supported on CNTs",level:"1"},{id:"sec_13_2",title:"3.1. Formation of metal NPs directly on CNTs",level:"2"},{id:"sec_13_3",title:"3.1.1. Physical methods",level:"3"},{id:"sec_14_3",title:"3.1.2. Chemical methods",level:"3"},{id:"sec_14_4",title:"3.1.2.1. Impregnation method",level:"4"},{id:"sec_15_4",title:"3.1.2.2. Electrochemical method",level:"4"},{id:"sec_16_4",title:"3.1.2.3. Colloidal method",level:"4"},{id:"sec_17_4",title:"3.1.2.4. Ion-exchange method ",level:"4"},{id:"sec_18_4",title:"3.1.2.5. Microwave heated polyol method",level:"4"},{id:"sec_21_2",title:"3.2. Connecting metal NPs and CNTs",level:"2"},{id:"sec_21_3",title:"3.2.1. Covalent linkage",level:"3"},{id:"sec_22_3",title:"3.2.2. Hydrophobic interactions and hydrogen bonds",level:"3"},{id:"sec_23_3",title:"3.2.3. π-Stacking",level:"3"},{id:"sec_24_3",title:"3.2.4. Electrostatic interactions",level:"3"},{id:"sec_27",title:"4. Activity validation of the synthesized catalysts in a fuel cell operation",level:"1"},{id:"sec_27_2",title:"4.1. Synthesis of metal/CNT based MEA",level:"2"},{id:"sec_28_2",title:"4.2. 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Q.SacherE.\n\t\t\t\t\t2008 Strongly enhanced interaction between evaporated Pt nanoparticles and functionalized multiwalled carbon nanotubes via plasma surface modifications: effects of physical and chemical defects. Journal of Physical Chemistry C, 112\n\t\t\t\t\t11 4075-4082, 1932-7447'},{id:"B160",body:'YangW.WangX.YangF.YangC.YangX.\n\t\t\t\t\t2008 Carbon nanotubes decorated with Pt nanocubes by a noncovalent functionalization method and their role in oxygen reduction. Advanced Materials, 20\n\t\t\t\t\t13 2579-2587, 0935-9648'},{id:"B161",body:'YoshitakeT.ShimakawaY.KuroshimaS.KimuraH.IchihashiT.KudoY.\n\t\t\t\t\t2002 Preparation of fine platinum catalyst supported on single-wall carbon nanohorns for fuel cell application. Physica B, 323\n\t\t\t\t\t1-4 , 124-126, 0921-4526'},{id:"B162",body:'YuR. Q.ChenL. W.LiuQ. P.LinJ. Y.TanK. L.NgS. C.ChanH.XuG. Q.HorT.\n\t\t\t\t\t1998 Platinum deposition on carbon nanotubes via chemical modification. Chemistry of Materials, 10\n\t\t\t\t\t3 718-722, 0897-4756'},{id:"B163",body:'ZamudioA.EliasA. L.Rodriguez-ManzoJ. A.Lopez-UriasF.Rodriguez-GattornoG.LupoF.RuhleM.SmithD. J.TerronesH.DiazD.TerronesM.\n\t\t\t\t\t2006 Efficient anchoring of silver nanoparticles on N-Doped carbon nanotubes. Small, 2\n\t\t\t\t\t3 346-350, 1613-6810'},{id:"B164",body:'ZhangG. X.YangD. Q.SacherE.\n\t\t\t\t\t2007 X-ray photoelectron spectroscopic analysis of Pt nanoparticles on highly oriented pyrolytic graphite, using symmetric component line shapes. Journal of Physical Chemistry C, 111\n\t\t\t\t\t2 565-570, 1932-7447'},{id:"B165",body:'ZhangJ.ZouH.QingQ.YangY.LiQ.LiuZ.GuoZ. D.\n\t\t\t\t\t2003 Effect of chemical oxidation on the structure of single-walled carbon nanotubes. Journal of Physical Chemistry B, 107\n\t\t\t\t\t16 3712-3718, 1520-6106'},{id:"B166",body:'ZhaoY.FanL. Z.ZhongH. Z.LiY. F.YangS. H.\n\t\t\t\t\t2007 Platinum nanoparticle clusters immobilized on multiwalled carbon nanotubes: Electrodeposition and enhanced electrocatalytic activity for methanol oxidation. Advanced Functional Materials, 17\n\t\t\t\t\t9 1537-1541, 0161-6301X'},{id:"B167",body:'ZhaoZ. W.GuoZ. P.DingJ.WexlerD.MaZ. F.ZhangD. Y.LiuH. K.\n\t\t\t\t\t2006 Novel ionic liquid supported synthesis of platinum-based electrocatalysts on multiwalled carbon nanotubes. Electrochemistry Communications, 8\n\t\t\t\t\t2 245-250, 1388-2481'},{id:"B168",body:'ZhengH. T.LiY. L.ChenS. X.ShenP. K.\n\t\t\t\t\t2006 Effect of support on the activity of Pd electrocatalyst for ethanol oxidation. Journal of Power Sources, 163\n\t\t\t\t\t1 371-375, 0378-7753'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Zhongqing Jiang1",address:"",affiliation:'
1Department of Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang, 1China
1Department of Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang, 1China
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1. Introduction
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The use of social media is growing at a rapid pace and the twenty-first century could be described as the “boom” period for social networking. According to reports provided by Smart Insights, as at February 2019 there were over 3.484 billion social media users. The Smart Insight report indicates that the number of social media users is growing by 9% annually and this trend is estimated to continue. Presently the number of social media users represents 45% of the global population [1]. The heaviest users of social media are “digital natives”; the group of persons who were born or who have grown up in the digital era and are intimate with the various technologies and systems, and the “Millennial Generation”; those who became adults at the turn of the twenty-first century. These groups of users utilize social media platforms for just about anything ranging from marketing, news acquisition, teaching, health care, civic engagement, and politicking to social engagement.
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The unethical use of social media has resulted in the breach of individual privacy and impacts both physical and information security. Reports in 2019 [1], reveal that persons between the ages 8 and 11 years spend an average 13.5 hours weekly online and 18% of this age group are actively engaged on social media. Those between ages 12 and 15 spend on average 20.5 hours online and 69% of this group are active social media users. While children and teenagers represent the largest Internet user groups, for the most part they do not know how to protect their personal information on the Web and are the most vulnerable to cyber-crimes related to breaches of information privacy [2, 3].
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In today’s IT-configured society data is one of, if not the most, valuable asset for most businesses/organizations. Organizations and governments collect information via several means including invisible data gathering, marketing platforms and search engines such as Google [4]. Information can be attained from several sources, which can be fused using technology to develop complete profiles of individuals. The information on social media is very accessible and can be of great value to individuals and organizations for reasons such as marketing, etc.; hence, data is retained by most companies for future use.
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2. Privacy
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Privacy or the right to enjoy freedom from unauthorized intrusion is the negative right of all human beings. Privacy is defined as the right to be left alone, to be free from secret surveillance, or unwanted disclosure of personal data or information by government, corporation, or individual (dictionary.com). In this chapter we will define privacy loosely, as the right to control access to personal information. Supporters of privacy posit that it is a necessity for human dignity and individuality and a key element in the quest for happiness. According to Baase [5] in the book titled “A Gift of Fire: Social, Legal and Ethical Issues for Computing and the Internet,” privacy is the ability to control information about one’ s self as well as the freedom from surveillance from being followed, tracked, watched, and being eavesdropped on. In this regard, ignoring privacy rights often leads to encroachment on natural rights.
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Privacy, or even the thought that one has this right, leads to peace of mind and can provide an environment of solitude. This solitude can allow people to breathe freely in a space that is free from interference and intrusion. According to Richards and Solove [6], Legal scholar William Prosser argued that privacy cases can be classified into four related “torts,” namely:
Intrusion—this can be viewed as encroachment (physical or otherwise) on ones liberties/solitude in a highly offensive way.
Privacy facts—making public, private information about someone that is of no “legitimate concern” to anyone.
False light—making public false and “highly offensive” information about others.
Appropriation—stealing someone’s identity (name, likeness) to gain advantage without the permission of the individual.
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Technology, the digital age, the Internet and social media have redefined privacy however as surveillance is no longer limited to a certain pre-defined space and location. An understanding of the problems and dangers of privacy in the digital space is therefore the first step to privacy control. While there can be clear distinctions between informational privacy and physical privacy, as pointed out earlier, intrusion can be both physical and otherwise.
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This chapter will focus on informational privacy which is the ability to control access to personal information. We examine privacy issues in the social media context focusing primarily on personal information and the ability to control external influences. We suggest that breach of informational privacy can impact: solitude (the right to be left alone), intimacy (the right not to be monitored), and anonymity (the right to have no public personal identity and by extension physical privacy impacted). The right to control access to facts or personal information in our view is a natural, inalienable right and everyone should have control over who see their personal information and how it is disseminated.
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In May 2019 the General Data Protection Regulation (GDPR) clearly outlined that it is unlawful to process personal data without the consent of the individual (subject). It is a legal requirement under the GDPR that privacy notices be given to individuals that outline how their personal data will be processed and the conditions that must be met that make the consent valid. These are:
“Freely given—an individual must be given a genuine choice when providing consent and it should generally be unbundled from other terms and conditions (e.g., access to a service should not be conditional upon consent being given).”
“Specific and informed—this means that data subjects should be provided with information as to the identity of the controller(s), the specific purposes, types of processing, as well as being informed of their right to withdraw consent at any time.”
“Explicit and unambiguous—the data subject must clearly express their consent (e.g., by actively ticking a box which confirms they are giving consent—pre-ticked boxes are insufficient).”
“Under 13s—children under the age of 13 cannot provide consent and it is therefore necessary to obtain consent from their parents.”
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Arguments can be made that privacy is a cultural, universal necessity for harmonious relationships among human beings and creates the boundaries for engagement and disengagement. Privacy can also be viewed as instrumental good because it is a requirement for the development of certain kinds of human relationships, intimacy and trust [7]. However, achieving privacy is much more difficult in light of constant surveillance and the inability to determine the levels of interaction with various publics [7]. Some critics argue that privacy provides protection against anti-social behaviors such as trickery, disinformation and fraud, and is thought to be a universal right [5]. However, privacy can also be viewed as relative as privacy rules may differ based on several factors such as “climate, religion, technological advancement and political arrangements” [8, 9]. The need for privacy is an objective reality though it can be viewed as “culturally rational” where the need for personal privacy is viewed as relative based on culture. One example is the push by the government, businesses and Singaporeans to make Singapore a smart nation. According to GovTech 2018 reports there is a push by the government in Singapore to harness the data “new gold” to develop systems that can make life easier for its people. The [10] report points out that Singapore is using sensors robots Smart Water Assessment Network (SWAN) to monitor water quality in its reservoirs, seeking to build smart health system and to build a smart transportation system to name a few. In this example privacy can be describe as “culturally rational” and the rules in general could differ based on technological advancement and political arrangements.
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In today’s networked society it is naïve and ill-conceived to think that privacy is over-rated and there is no need to be concerned about privacy if you have done nothing wrong [5]. The effects of information flow can be complex and may not be simply about protection for people who have something to hide. Inaccurate information flow can have adverse long-term implications for individuals and companies. Consider a scenario where someone’s computer or tablet is stolen. The perpetrator uses identification information stored on the device to access their social media page which could lead to access to their contacts, friends and friends of their “friends” then participate in illegal activities and engage in anti-social activities such as hacking, spreading viruses, fraud and identity theft. The victim is now in danger of being accused of criminal intentions, or worse. These kinds of situations are possible because of technology and networked systems. Users of social media need to be aware of the risks that are associated with participation.
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3. Social media
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The concept of social networking pre-dates the Internet and mass communication as people are said to be social creatures who when working in groups can achieve results in a value greater than the sun of its parts [11]. The explosive growth in the use of social media over the past decade has made it one of the most popular Internet services in the world, providing new avenues to “see and be seen” [12, 13]. The use of social media has changed the communication landscape resulting in changes in ethical norms and behavior. The unprecedented level of growth in usage has resulted in the reduction in the use of other media and changes in areas including civic and political engagement, privacy and safety [14]. Alexa, a company that keeps track of traffic on the Web, indicates that as of August, 2019 YouTube, Facebook and Twitter are among the top four (4) most visited sites with only Google, being the most popular search engine, surpassing these social media sites.
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Social media sites can be described as online services that allow users to create profiles which are “public, semi-public” or both. Users may create individual profiles and/or become a part of a group of people with whom they may be acquainted offline [15]. They also provide avenues to create virtual friendships. Through these virtual friendships, people may access details about their contacts ranging from personal background information and interests to location. Social networking sites provide various tools to facilitate communication. These include chat rooms, blogs, private messages, public comments, ways of uploading content external to the site and sharing videos and photographs. Social media is therefore drastically changing the way people communicate and form relationships.
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Today social media has proven to be one of the most, if not the most effective medium for the dissemination of information to various audiences. The power of this medium is phenomenal and ranges from its ability to overturn governments (e.g., Moldova), to mobilize protests, assist with getting support for humanitarian aid, organize political campaigns, organize groups to delay the passing of legislation (as in the case with the copyright bill in Canada) to making social media billionaires and millionaires [16, 17]. The enabling nature and the structure of the media that social networking offers provide a wide range of opportunities that were nonexistent before technology. Facebook and YouTube marketers and trainers provide two examples. Today people can interact with and learn from people millions of miles away. The global reach of this medium has removed all former pre-defined boundaries including geographical, social and any other that existed previously. Technological advancements such as Web 2.0 and Web 4.0 which provide the framework for collaboration, have given new meaning to life from various perspectives: political, institutional and social.
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4. Privacy and social media
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Social medial and the information/digital era have “redefined” privacy. In today’s Information Technology—configured societies, where there is continuous monitoring, privacy has taken on a new meaning. Technologies such as closed-circuit cameras (CCTV) are prevalent in public spaces or in some private spaces including our work and home [7, 18]. Personal computers and devices such as our smart phones enabled with Global Positioning System (GPS), Geo locations and Geo maps connected to these devices make privacy as we know it, a thing of the past. Recent reports indicate that some of the largest companies such as Amazon, Microsoft and Facebook as well as various government agencies are collecting information without consent and storing it in databases for future use. It is almost impossible to say privacy exists in this digital world (@nowthisnews).
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The open nature of the social networking sites and the avenues they provide for sharing information in a “public or semi-public” space create privacy concerns by their very construct. Information that is inappropriate for some audiences are many times inadvertently made visible to groups other than those intended and can sometimes result in future negative outcomes. One such example is a well-known case recorded in an article entitled “The Web Means the End of Forgetting” that involved a young woman who was denied her college license because of backlash from photographs posted on social media in her private engagement.
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Technology has reduced the gap between professional and personal spaces and often results in information exposure to the wrong audience [19]. The reduction in the separation of professional and personal spaces can affect image management especially in a professional setting resulting in the erosion of traditional professional image and impression management. Determining the secondary use of personal information and those who have access to this information should be the prerogative of the individual or group to whom the information belongs. However, engaging in social media activities has removed this control.
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Privacy on social networking sites (SNSs) is heavily dependent on the users of these networks because sharing information is the primary way of participating in social communities. Privacy in SNSs is “multifaceted.” Users of these platforms are responsible for protecting their information from third-party data collection and managing their personal profiles. However, participants are usually more willing to give personal and more private information in SNSs than anywhere else on the Internet. This can be attributed to the feeling of community, comfort and family that these media provide for the most part. Privacy controls are not the priority of social networking site designers and only a small number of the young adolescent users change the default privacy settings of their accounts [20, 21]. This opens the door for breaches especially among the most vulnerable user groups, namely young children, teenagers and the elderly. The nature of social networking sites such as Facebook and Twitter and other social media platforms cause users to re-evaluate and often change their personal privacy standards in order to participate in these social networked communities [13].
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While there are tremendous benefits that can be derived from the effective use of social media there are some unavoidable risks that are involved in its use. Much attention should therefore be given to what is shared in these forums. Social platforms such as Facebook, Twitter and YouTube are said to be the most effective media to communicate to Generation Y’s (Gen Y’s), as teens and young adults are the largest user groups on these platforms [22]. However, according to Bolton et al. [22] Gen Y’s use of social media, if left unabated and unmonitored will have long-term implications for privacy and engagement in civic activities as this continuous use is resulting in changes in behavior and social norms as well as increased levels of cyber-crime.
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Today social networks are becoming the platform of choice for hackers and other perpetrators of antisocial behavior. These media offer large volumes of data/information ranging from an individual’s date of birth, place of residence, place of work/business, to information about family and other personal activities. In many cases users unintentionally disclose information that can be both dangerous and inappropriate. Information regarding activities on social media can have far reaching negative implications for one’s future. A few examples of situations which can, and have been affected are employment, visa acquisition, and college acceptance. Indiscriminate participation has also resulted in situations such identity theft and bank fraud just to list a few. Protecting privacy in today’s networked society can be a great challenge. The digital revolution has indeed distorted our views of privacy, however, there should be clear distinctions between what should be seen by the general public and what should be limited to a selected group. One school of thought is that the only way to have privacy today is not to share information in these networked communities. However, achieving privacy and control over information flows and disclosure in networked communities is an ongoing process in an environment where contexts change quickly and are sometimes blurred. This requires intentional construction of systems that are designed to mitigate privacy issues [13].
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5. Ethics and social media
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Ethics can be loosely defined as “the right thing to do” or it can be described as the moral philosophy of an individual or group and usually reflects what the individual or group views as good or bad. It is how they classify particular situations by categorizing them as right or wrong. Ethics can also be used to refer to any classification or philosophy of moral values or principles that guides the actions of an individual or group [23]. Ethical values are intended to be guiding principles that if followed, could yield harmonious results and relationships. They seek to give answers to questions such as “How should I be living? How do I achieve the things that are deemed important such as knowledge and happiness or the acquisition of attractive things?” If one chooses happiness, the next question that needs to be answered is “Whose happiness should it be; my own happiness or the happiness of others?” In the domain of social media, some of the ethical questions that must be contemplated and ultimately answered are [24]:
Can this post be regarded as oversharing?
Has the information in this post been distorted in anyway?
What impact will this post have on others?
\n\n
As previously mentioned, users within the ages 8–15 represent one of the largest social media user groups. These young persons within the 8–15 age range are still learning how to interact with the people around them and are deciding on the moral values that they will embrace. These moral values will help to dictate how they will interact with the world around them. The ethical values that guide our interactions are usually formulated from some moral principle taught to us by someone or a group of individuals including parents, guardians, religious groups, and teachers just to name a few. Many of the Gen Y’s/“Digital Babies” are “newbies” yet are required to determine for themselves the level of responsibility they will display when using the varying social media platforms. This includes considering the impact a post will have on their lives and/or the lives of other persons. They must also understand that when they join a social media network, they are joining a community in which certain behavior must be exhibited. Such responsibility requires a much greater level of maturity than can be expected from them at that age.
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It is not uncommon for individuals to post even the smallest details of their lives from the moment they wake up to when they go to bed. They will openly share their location, what they eat at every meal or details about activities typically considered private and personal. They will also share likes and dislikes, thoughts and emotional states and for the most part this has become an accepted norm. Often times however, these shares do not only contain information about the person sharing but information about others as well. Many times, these details are shared on several social media platforms as individuals attempt to ensure that all persons within their social circle are kept updated on their activities. With this openness of sharing risks and challenges arise that are often not considered but can have serious impacts. The speed and scale with which social media creates information and makes it available—almost instantaneously—on a global scale, added to the fact that once something is posted there is really no way of truly removing it, should prompt individuals to think of the possible impact a post can have. Unfortunately, more often than not, posts are made without any thought of the far-reaching impact they can have on the lives of the person posting or others that may be implicated by the post.
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6. Why do people share?
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According to Berger and Milkman [25] there are five (5) main reasons why users are compelled to share content online, whether it is every detail or what they deem as highlights of their lives. These are:
cause related
personal connection to content
to feel more involved in the world
to define who they are
to inform and entertain
\n\n
People generally share because they believe that what they are sharing is important. It is hoped that the shared content will be deemed important to others which will ultimately result in more shares, likes and followers.
\n
\nFigure 1 below sums up the findings of Berger and Milkman [25] which shows that the main reason people feel the need to share content on the varying social media platform is that the content relates to what is deemed as worthy cause. 84% of respondents highlighted this as the primary motivation for sharing. Seventy-eight percent said that they share because they feel a personal connection to the content while 69 and 68%, respectively said the content either made them feel more involved with the world or helped them to define who they were. Forty-nine percent share because of the entertainment or information value of the content. A more in depth look at each reason for sharing follows.
\n
Figure 1.
Why people share source: Global Social Media Research. \nthesocialmediahat.com\n [26].
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7. Content related to a cause
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Social media has provided a platform for people to share their thoughts and express concerns with others for what they regard as a worthy cause. Cause related posts are dependent on the interest of the individual. Some persons might share posts related to causes and issues happening in society. In one example, the parents of a baby with an aggressive form of leukemia, who having been told that their child had only 3 months to live unless a suitable donor for a blood stem cell transplant could be found, made an appeal on social media. The appeal was quickly shared and a suitable donor was soon found. While that was for a good cause, many view social media merely as platforms for freedom of speech because anyone can post any content one creates. People think the expression of their thoughts on social media regarding any topic is permissible. The problem with this is that the content may not be accepted by law or it could violate the rights of someone thus giving rise to ethical questions.
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8. Content with a personal connection
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When social media users feel a personal connection to their content, they are more inclined to share the content within their social circles. This is true of information regarding family and personal activities. Content created by users also invokes a deep feeling of connection as it allows the users to tell their stories and it is natural to want the world or at least friends to know of the achievement. This natural need to share content is not new as humans have been doing this in some form or the other, starting with oral history to the media of the day; social media. Sharing the self-created content gives the user the opportunity of satisfying some fundamental needs of humans to be heard, to matter, to be understood and emancipated. The problem with this however is that in an effort to gratify the fundamental needs, borders are crossed because the content may not be sharable (can this content be shared within the share network?), it may not be share-worthy (who is the audience that would appreciate this content?) or it may be out of context (does the content fit the situation?).
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9. Content that makes them feel more involved in the world
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One of the driving factors that pushes users to share content is the need to feel more in tune with the world around them. This desire is many times fueled by jealousy. Many social media users are jealous when their friends’ content gets more attention than their own and so there is a lot of pressure to maintain one’s persona in social circles, even when the information is unrealistic, as long as it gets as much attention as possible. Everything has to be perfect. In the case of a photo, for example, there is lighting, camera angle and background to consider. This need for perfection puts a tremendous amount of pressure on individuals to ensure that posted content is “liked” by friends. They often give very little thought to the amount of their friend’s work that may have gone on behind the scenes to achieve that perfect social post.
\n
Social media platforms have provided everyone with a forum to express views, but, as a whole, conversations are more polarized, tribal and hostile. With Facebook for instance, there has been a huge uptick in fake news, altered images, dangerous health claims and cures, and the proliferation of anti-science information. This is very distressing and disturbing because people are too willing to share and to believe without doing their due diligence and fact-checking first.
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10. Content that defines who they are
\n
Establishing one’s individuality in society can be challenging for some persons because not everyone wants to fit in. Some individuals will do all they can to stand out and be noticed. Social media provides the avenue for exposure and many individuals will seek to leverage the media to stand out of the crowd and not just be a fish in the school. Today many young people are currently being brought up in a culture that defines people by their presence on social media where in previous generations, persons were taught to define themselves by their career choices. These lessons would start from childhood by asking children what they wanted to be when they grew up and then rewarding them based on the answers they give [27]. In today’s digital era, however, social media postings and the number of “likes” or “dislikes” they attract, signal what is appealing to others. Therefore, post that are similar to those that receive a large number of likes but which are largely unrealistic are usually made for self-gratification.
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11. Content that informs and entertains
\n
The acquisition of knowledge and skills is a vital part of human survival and social media has made this process much easier. It is not uncommon to hear persons realizing that they need a particular knowledge set that they do not possess say “I need to lean to do this. I’ll just YouTube it.” Learning and adapting to change in as short as possible time is vital in today’s society and social media coupled with the Internet put it all at the finger tips. Entertainment has the ability to bring people together and is a good way for people to bond. It provides a diversion from the demands of life and fills leisure time with amusement. Social media is an outlet for fun, pleasurable and enjoyable activities that are so vital to human survival [28]. It is now common place to see persons watching a video, viewing images and reading text that is amusing on any of the available social media platforms. Quite often these videos, images and texts can be both informative and entertaining, but there can be problems however as at times they can cross ethical lines that can lead to conflict.
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12. Ethical challenges with social media use
\n
The use of modern-day technology has brought several benefits. Social media is no different and chief amongst its benefit is the ability to stay connected easily and quickly as well as build relationships with people with similar interests. As with all technology, there are several challenges that can make the use of social media off putting and unpleasant. Some of these challenges appear to be minor but they can have far reaching effects into the lives of the users of social media and it is therefore advised that care be taken to minimize the challenges associated with the use of social media [29].
\n
A major challenge with the use of social media is oversharing because when persons share on social media, they tend to share as much as is possible which is often times too much [24]. When persons are out and about doing exciting things, it is natural to want to share this with the world as many users will post a few times a day when they head to lunch, visit a museum, go out to dinner or other places of interest [30]. While this all seems relatively harmless, by using location-based services which pinpoint users with surprising accuracy and in real time, users place themselves in danger of laying out a pattern of movement that can be easily traced. While this seems more like a security or privacy issue it stems from an ethical dilemma—“Am I sharing too much?” Oversharing can also lead to damage of user’s reputation especially if the intent is to leverage the platform for business [24]. Photos of drunken behavior, drug use, partying or other inappropriate content can change how you are viewed by others.
\n
Another ethical challenge users of social media often encounter is that they have no way of authenticating content before sharing, which becomes problematic when the content paints people or establishments negatively. Often times content is shared with them by friends, family and colleagues. The unauthenticated content is then reshared without any thought but sometimes this content may have been maliciously altered so the user unknowingly participates in maligning others. Even if the content is not altered the fact that the content paints someone or something in a bad light should send off warning bells as to whether or not it is right to share the content which is the underlying principle of ethical behavior.
\n
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13. Conflicting views
\n
Some of the challenges experienced by social media posts are a result of a lack of understanding and sometimes a lack of respect for the varying ethical and moral standpoints of the people involved. We have established that it is typical for persons to post to social media sites without any thought as to how it can affect other persons, but many times these posts are a cause of conflict because of a difference of opinion that may exist and the effect the post may have. Each individual will have his or her own ethical values and if they differ then this can result in conflict [31]. When an executive of a British company made an Instagram post with some racial connotations before boarding a plane to South Africa it started a frenzy that resulted in the executive’s immediate dismissal. Although the executive said it was a joke and there was no prejudice intended, this difference in views as to the implications of the post, resulted in an out of work executive and a company scrambling to maintain its public image.
\n
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14. Impact on personal development
\n
In this age of sharing, many young persons spend a vast amount of time on social media checking the activities of their “friends” as well as posting on their own activities so their “friends” are aware of what they are up to. Apart from interfering with their academic progress, time spent on these posts at can have long term repercussions. An example is provided by a student of a prominent university who posted pictures of herself having a good time at parties while in school. She was denied employment because of some of her social media posts. While the ethical challenge here is the question of the employee’s right to privacy and whether the individual’s social media profile should affect their ability to fulfill their responsibilities as an employee, the impact on the individual’s long term personal growth is clear.
\n
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15. Conclusion
\n
In today’s information age, one’s digital footprint can make or break someone; it can be the deciding factor on whether or not one achieves one’s life-long ambitions. Unethical behavior and interactions on social media can have far reaching implications both professionally and socially. Posting on the Internet means the “end of forgetting,” therefore, responsible use of this medium is critical. The unethical use of social media has implications for privacy and can result in security breaches both physically and virtually. The use of social media can also result in the loss of privacy as many users are required to provide information that they would not divulge otherwise. Social media use can reveal information that can result in privacy breaches if not managed properly by users. Therefore, educating users of the risks and dangers of the exposure of sensitive information in this space, and encouraging vigilance in the protection of individual privacy on these platforms is paramount. This could result in the reduction of unethical and irresponsible use of these media and facilitate a more secure social environment. The use of social media should be governed by moral and ethical principles that can be applied universally and result in harmonious relationships regardless of race, culture, religious persuasion and social status.
\n
Analysis of the literature and the findings of this research suggest achieving acceptable levels of privacy is very difficult in a networked system and will require much effort on the part of individuals. The largest user groups of social media are unaware of the processes that are required to reduce the level of vulnerability of their personal data. Therefore, educating users of the risk of participating in social media is the social responsibility of these social network platforms. Adapting universally ethical behaviors can mitigate the rise in the number of privacy breaches in the social networking space. This recommendation coincides with philosopher Immanuel Kant’s assertion that, the Biblical principle which states “Do unto others as you have them do unto you” can be applied universally and should guide human interactions [5]. This principle, if adhered to by users of social media and owners of these platforms could raise the awareness of unsuspecting users, reduce unethical interactions and undesirable incidents that could negatively affect privacy, and by extension security in this domain.
\n
\n\n',keywords:"privacy, ethics, social media",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/70973.pdf",chapterXML:"https://mts.intechopen.com/source/xml/70973.xml",downloadPdfUrl:"/chapter/pdf-download/70973",previewPdfUrl:"/chapter/pdf-preview/70973",totalDownloads:937,totalViews:0,totalCrossrefCites:0,dateSubmitted:"September 11th 2019",dateReviewed:"December 19th 2019",datePrePublished:"February 5th 2020",datePublished:"September 9th 2020",dateFinished:null,readingETA:"0",abstract:"Today’s information/digital age offers widespread use of social media. The use of social media is ubiquitous and cuts across all age groups, social classes and cultures. However, the increased use of these media is accompanied by privacy issues and ethical concerns. These privacy issues can have far-reaching professional, personal and security implications. Ultimate privacy in the social media domain is very difficult because these media are designed for sharing information. Participating in social media requires persons to ignore some personal, privacy constraints resulting in some vulnerability. The weak individual privacy safeguards in this space have resulted in unethical and undesirable behaviors resulting in privacy and security breaches, especially for the most vulnerable group of users. An exploratory study was conducted to examine social media usage and the implications for personal privacy. We investigated how some of the requirements for participating in social media and how unethical use of social media can impact users’ privacy. Results indicate that if users of these networks pay attention to privacy settings and the type of information shared and adhere to universal, fundamental, moral values such as mutual respect and kindness, many privacy and unethical issues can be avoided.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/70973",risUrl:"/chapter/ris/70973",signatures:"Nadine Barrett-Maitland and Jenice Lynch",book:{id:"8423",title:"Security and Privacy From a Legal, Ethical, and Technical Perspective",subtitle:null,fullTitle:"Security and Privacy From a Legal, Ethical, and Technical Perspective",slug:"security-and-privacy-from-a-legal-ethical-and-technical-perspective",publishedDate:"September 9th 2020",bookSignature:"Christos Kalloniatis and Carlos Travieso-Gonzalez",coverURL:"https://cdn.intechopen.com/books/images_new/8423.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"219671",title:"Associate Prof.",name:"Christos",middleName:null,surname:"Kalloniatis",slug:"christos-kalloniatis",fullName:"Christos Kalloniatis"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:[{id:"311821",title:"Ph.D. Student",name:"Nadine",middleName:null,surname:"Barrett-Maitland",fullName:"Nadine Barrett-Maitland",slug:"nadine-barrett-maitland",email:"nadinemland@yahoo.com",position:null,institution:null},{id:"311822",title:"Ms.",name:"Jenice",middleName:null,surname:"Lynch",fullName:"Jenice Lynch",slug:"jenice-lynch",email:"neecy.lyn@gmail.com",position:null,institution:{name:"University of Technology, Jamaica",institutionURL:null,country:{name:"Jamaica"}}}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Privacy",level:"1"},{id:"sec_3",title:"3. Social media",level:"1"},{id:"sec_4",title:"4. Privacy and social media",level:"1"},{id:"sec_5",title:"5. Ethics and social media",level:"1"},{id:"sec_6",title:"6. Why do people share?",level:"1"},{id:"sec_7",title:"7. Content related to a cause",level:"1"},{id:"sec_8",title:"8. Content with a personal connection",level:"1"},{id:"sec_9",title:"9. Content that makes them feel more involved in the world",level:"1"},{id:"sec_10",title:"10. Content that defines who they are",level:"1"},{id:"sec_11",title:"11. Content that informs and entertains",level:"1"},{id:"sec_12",title:"12. Ethical challenges with social media use",level:"1"},{id:"sec_13",title:"13. Conflicting views",level:"1"},{id:"sec_14",title:"14. Impact on personal development",level:"1"},{id:"sec_15",title:"15. Conclusion",level:"1"}],chapterReferences:[{id:"B1",body:'\nChaffey D. Global Social Media Research. Smart Insights. 2019. Retrieved from: https://www.smartinsights.com/social-media-marketing/social-media-strategy/new-global-social-media-research/\n\n'},{id:"B2",body:'\nSmartSocial. Teen Social Media Statistics (What Parents Need to Know). 2019. Retrieved from: https://smartsocial.com/social-media-statistics/\n\n'},{id:"B3",body:'\nWisniewski P, Jia H, Xu H, Rosson MB, Carroll JM. Preventative vs. reactive: How parental mediation influences teens’ social media privacy behaviors. In: Proceedings of the 18th ACM Conference on Computer Supported Cooperative Work and Social Computing; ACM; 2015. pp. 302-316\n'},{id:"B4",body:'\nChai S, Bagchi-Sen S, Morrell C, Rao HR, Upadhyaya SJ. Internet and online information privacy: An exploratory study of preteens and early teens. IEEE Transactions on Professional Communication. 2009;52(2):167-182\n'},{id:"B5",body:'\nBaase S. A Gift of Fire. Upper Saddle River, New Jersey: Pearson Education Limited (Prentice Hall); 2012\n'},{id:"B6",body:'\nRichards NM, Solove DJ. Prosser’s privacy law: A mixed legacy. California Law Review. 2010;98:1887\n'},{id:"B7",body:'\nJohnson DG. Computer ethics. In: The Blackwell Guide to the Philosophy of Computing and Information. Upper Saddle River, New Jersey: Pearson Education (Prentice Hall); 2004. pp. 65-75\n'},{id:"B8",body:'\nCohen JE. What privacy is for. Harvard Law Review. 2012;126:1904\n'},{id:"B9",body:'\nMoore AD. Toward informational privacy rights. San Diego Law Review. 2007;44:809\n'},{id:"B10",body:'\nGOVTECH. Singapore. 2019. Retrieved from: https://www.tech.gov.sg/products-and-services/smart-nation-sensor-platform/\n\n'},{id:"B11",body:'\nWeaver AC, Morrison BB. Social networking. Computer. 2008;41(2):97-100\n'},{id:"B12",body:'\nBoulianne S. Social media use and participation: A meta-analysis of current research. Information, Communication and Society. 2015;18(5):524-538\n'},{id:"B13",body:'\nMarwick AE, Boyd D. Networked privacy: How teenagers negotiate context in social media. New Media & Society. 2014;16(7):1051-1067\n'},{id:"B14",body:'\nMcCay-Peet L, Quan-Haase A. What is social media and what questions can social media research help us answer. In: The SAGE Handbook of Social Media Research Methods. Thousand Oaks, CA: SAGE Publishers; 2017. pp. 13-26\n'},{id:"B15",body:'\nGil de Zúñiga H, Jung N, Valenzuela S. Social media use for news and individuals’ social capital, civic engagement and political participation. Journal of Computer-Mediated Communication. 2012;17(3):319-336\n'},{id:"B16",body:'\nEms L. Twitter’s place in the tussle: How old power struggles play out on a new stage. Media, Culture and Society. 2014;36(5):720-731\n'},{id:"B17",body:'\nHaggart B. Fair copyright for Canada: Lessons for online social movements from the first Canadian Facebook uprising. Canadian Journal of Political Science (Revue canadienne de science politique). 2013;46(4):841-861\n'},{id:"B18",body:'\nAndrews LB. I Know Who You are and I Saw What You Did: Social Networks and the Death of Privacy. Simon and Schuster, Free Press; 2012\n'},{id:"B19",body:'\nEchaiz J, Ardenghi JR. Security and online social networks. In: XV Congreso Argentino de Ciencias de la Computación. 2009\n'},{id:"B20",body:'\nBarrett-Maitland N, Barclay C, Osei-Bryson KM. Security in social networking services: A value-focused thinking exploration in understanding users’ privacy and security concerns. Information Technology for Development. 2016;22(3):464-486\n'},{id:"B21",body:'\nVan Der Velden M, El Emam K. “Not all my friends need to know”: A qualitative study of teenage patients, privacy, and social media. Journal of the American Medical Informatics Association. 2013;20(1):16-24\n'},{id:"B22",body:'\nBolton RN, Parasuraman A, Hoefnagels A, Migchels N, Kabadayi S, Gruber T, et al. Understanding Generation Y and their use of social media: A review and research agenda. Journal of Service Management. 2013;24(3):245-267\n'},{id:"B23",body:'\nCohn C. Social Media Ethics and Etiquette. CompuKol Communication LLC. 20 March 2010. Retrieved from: https://www.compukol.com/social-media-ethics-and-etiquette/\n\n'},{id:"B24",body:'\nNates C. The Dangers of Oversharing of Social Media. Pure Moderation. 2018. Retrieved from: https://www.puremoderation.com/single-post/The-Dangers-of-Oversharing-on-Social-Media\n\n'},{id:"B25",body:'\nBerger J, Milkman K. What makes online content go viral. Journal of Marketing Research. 2011;49(2):192-205\n'},{id:"B26",body:'\nThe Social Media Hat. How to Find Amazing Content for Your Social Media Calendar (And Save Yourself Tons of Work). 29 August 2016. Retrieved from: https://www.thesocialmediahat.com/blog/how-to-find-amazing-content-for-your-social-media-calendar-and-save-yourself-tons-of-work/\n\n'},{id:"B27",body:'\nPeople First. Does what you do define who you are. 15 September 2012. Retrieved from: https://blog.peoplefirstps.com/connect2lead/what-you-do-define-you\n\n'},{id:"B28",body:'\nDreyfus E. Does what you do define who you are. Psychologically Speaking. 2010. Retrieved from: https://www.edwarddreyfusbooks.com/psychologically-speaking/does-what-you-do-define-who-you-are/\n\n'},{id:"B29",body:'\nBusiness Ethics Briefing. The Ethical Challenges and Opportunities of Social Media Use. (Issue 66). 2019. Retrieved from: https://www.ibe.org.uk/userassets/briefings/ibe_social_media_briefing.pdf\n\n'},{id:"B30",body:'\nStaff Writer. The consequences of oversharing on social networks. Reputation Defender. 2018. Retrieved from: https://www.reputationdefender.com/blog/social-media/consequences-oversharing-social-networks\n\n'},{id:"B31",body:'\nBusiness Ethics Briefing. The Ethical Challenges of Social Media. (Issue 22). 2011. Retrieved from: https://www.ibe.org.uk/userassets/briefings/ibe_briefing_22_the_ethical_challenges_of_social_media.pdf\n\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Nadine Barrett-Maitland",address:"nadinemland@yahoo.com",affiliation:'
'}],corrections:null},book:{id:"8423",title:"Security and Privacy From a Legal, Ethical, and Technical Perspective",subtitle:null,fullTitle:"Security and Privacy From a Legal, Ethical, and Technical Perspective",slug:"security-and-privacy-from-a-legal-ethical-and-technical-perspective",publishedDate:"September 9th 2020",bookSignature:"Christos Kalloniatis and Carlos Travieso-Gonzalez",coverURL:"https://cdn.intechopen.com/books/images_new/8423.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"219671",title:"Associate Prof.",name:"Christos",middleName:null,surname:"Kalloniatis",slug:"christos-kalloniatis",fullName:"Christos Kalloniatis"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}}},profile:{item:{id:"198219",title:"Dr.",name:"Marcelo",middleName:null,surname:"Nociari",email:"mnociari@med.cornell.edu",fullName:"Marcelo Nociari",slug:"marcelo-nociari",position:null,biography:null,institutionString:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",totalCites:0,totalChapterViews:"0",outsideEditionCount:0,totalAuthoredChapters:"1",totalEditedBooks:"0",personalWebsiteURL:null,twitterURL:null,linkedinURL:null,institution:{name:"Weill Cornell Medical College in Qatar",institutionURL:null,country:{name:"Qatar"}}},booksEdited:[],chaptersAuthored:[{title:"Lipofuscin Accumulation into and Clearance from Retinal Pigment Epithelium Lysosomes: Physiopathology and Emerging Therapeutics",slug:"lipofuscin-accumulation-into-and-clearance-from-retinal-pigment-epithelium-lysosomes-physiopathology",abstract:"Photoreceptors undergo a constant renewal of their light sensitive outer segments (POSs). In the renewal process, 10% of the POS mass is daily phagocytized by the adjacent retinal pigment epithelium (RPE). POS contain vast amounts of 11-cis retinal and all-trans-retinal, two highly reactive vitamin A aldehydes that spontaneously dimerize into lipid bisretinoids (LBs) and accumulate into RPE lysosomes during phagocytosis. As LBs are refractory to lysosomal hydrolases and RPE cells do not divide, this accumulation is irreversible and results in the formation of lipofuscin granules. Lipofuscin accumulation is toxic for RPE cells through a variety of light-dependent and light-independent mechanisms. Beyond a threshold, RPE cells die resulting in secondary loss of overlying photoreceptors. Currently, there are no effective treatments for retinal disorders associated with genetic or age-associated LB accumulation, such as Stargardt disease and age-related macular degeneration (AMD). Thus, there is a great need for medical interventions. Here, we discuss the current understanding of lipofuscin's pathogenicity and the status of different strategies under development to promote LB elimination from RPE lysosomes.",signatures:"Marcelo M. 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If your research is financed through any of the below-mentioned funders, please consult their Open Access policies or grant ‘terms and conditions’ to explore ways to cover your publication costs (also accessible by clicking on the link in their title).
\n\n
IMPORTANT: You must be a member or grantee of the listed funders in order to apply for their Open Access publication funds. Do not attempt to contact the funders if this is not the case.
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UK Research and Innovation (former Research Councils UK (RCUK) - including AHRC, BBSRC, ESRC, EPSRC, MRC, NERC, STFC.) Processing charges for books/book chapters can be covered through RCUK block grants which are allocated to most universities in the UK, which then handle the OA publication funding requests. It is at the discretion of the university whether it will approve the request.)
UK Research and Innovation (former Research Councils UK (RCUK) - including AHRC, BBSRC, ESRC, EPSRC, MRC, NERC, STFC.) Processing charges for books/book chapters can be covered through RCUK block grants which are allocated to most universities in the UK, which then handle the OA publication funding requests. It is at the discretion of the university whether it will approve the request.)
Wellcome Trust (Funding available only to Wellcome-funded researchers/grantees)
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