Preparative methods of cellulose/metal nanocomposites.
\r\n\tBacteriology is subdivision of microbiology which deals with morphology, ecology and biotechnology of bacteria that found in different environmental niches - either inside living organisms, or free living in soil, marine and fresh water. It is also connected to medicine concerning spoilage of foods and bacterial associated diseases (pathogenic bacteriology). On the other hand, good use of friendly bacteria gives protection from other bad microbes causing serious illness. These beneficial bacteria promote absorption of nutrients and aid in healthy digestion.
\r\n\r\n\tBacteria are key players in bioremediation.They can play a significant role in the mitigation or removal of contaminants in the environment, both organic and inorganic.
\r\n\r\n\tIn natural environment, bacteria produce nanoparticles as part of their metabolism. Bacteria grab target ions from their environment and then turn the metal ions into the element metal through enzymes generated by the cell activities.The biosynthesized nanoparticles have been used in a variety of applications including drug carriers for targeted delivery, cancer treatment, gene therapy and DNA analysis, antibacterial agents, biosensors and magnetic resonance imaging (MRI).
\r\n\r\n\tThis book intends to provide the reader with a comprehensive overview of bacterial science and it's applications in different disciplines.
",isbn:null,printIsbn:null,pdfIsbn:null,doi:null,price:0,priceEur:null,priceUsd:null,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"9efd2538a169c261ee567026dc837dd2",bookSignature:"Dr. Khouloud Mohamed Barakat",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/7508.jpg",keywords:"Prokaryotes, Archaea, Bacteria, Microbial Growth, Control, Bacterial Flora, Soil Bacteria, Marine Bacteria, Pathogenic Bacteria, Benefit Bacteria, Industrial Bacteria, Bacterial Biotechnology, Bacterial Nanotechnology",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 15th 2018",dateEndSecondStepPublish:"June 5th 2018",dateEndThirdStepPublish:"August 4th 2018",dateEndFourthStepPublish:"October 23rd 2018",dateEndFifthStepPublish:"December 22nd 2018",remainingDaysToSecondStep:"3 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"218571",title:"Dr.",name:"Khouloud Mohamed",middleName:null,surname:"Barakat",slug:"khouloud-mohamed-barakat",fullName:"Khouloud Mohamed Barakat",profilePictureURL:"https://mts.intechopen.com/storage/users/218571/images/system/218571.jpeg",biography:"Associate Professor in Microbiology LAB., National Institute of Oceanography and Fisheries, Alexandria Egypt. She received her BSc in Microbiology, MSc and Ph.D. in Marine Microbiology from Faculty of Science, Alexandria University in 1998, 2003 and 2008, respectively. She had 25 published papers in local and international peer-reviewed journals and 2 abstracts conference proceedings in the field of marine and microbial biotechnology. She worked as an Assistant Professor at Faculty of Science and Humanities studies, Shaqra University, Saudi Arabia, from 2010 -2012 where she conducted lectures on General Microbiology, Bacteriology and Pollution. She is a member of numerous local societies and serves as an editorial board of the International Journal of Scientific and Technology Research, International Archive of Medicine, Lawarence Press, International Journal of Natural Resource Ecology and Management. She was also selected as a member at Who\\'s Who in the World for inclusion in the forthcoming 31st Edition 2014. She supervised many PhD and MSc thesis and performed more than 15 arbitration of scientific research and thesis.",institutionString:"National Institute of Oceanography and Fisheries",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"National Institute of Oceanography and Fisheries",institutionURL:null,country:{name:"Egypt"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"409",title:"Bacteriology",slug:"biochemistry-genetics-and-molecular-biology-microbiology-bacteriology"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"280415",firstName:"Josip",lastName:"Knapic",middleName:null,title:"Mr.",imageUrl:"https://mts.intechopen.com/storage/users/280415/images/8050_n.jpg",email:"josip@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copy-editing and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"2796",title:"Lactic Acid Bacteria",subtitle:"R & D for Food, Health and Livestock Purposes",isOpenForSubmission:!1,hash:"8d625f084ccba1e96cc326406074fe3f",slug:"lactic-acid-bacteria-r-d-for-food-health-and-livestock-purposes",bookSignature:"Marcelino Kongo",coverURL:"https://cdn.intechopen.com/books/images_new/2796.jpg",editedByType:"Edited by",editors:[{id:"138356",title:"Dr.",name:"J. Marcelino",surname:"Kongo",slug:"j.-marcelino-kongo",fullName:"J. 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In particular, extensive work has been undertaken in the development of sustainable and environmentally friendly resources and methods. A key idea has been the production of nanocomposites comprising biopolymers that in specific contexts can replace conventional materials such as synthetic polymers. It is well known that the properties of nanocomposite materials depend not only on the properties of their individual components but also on morphological and interfacial characteristics arising from the combination of distinct materials [1]. Therefore the use of polymers such as cellulose, starch, alginate, dextran, carrageenan, and chitosan among others, gain great relevance not only due to their renewable nature and biodegradability, but also because a variety of formulations can be exploited depending on the envisaged functionality [2, 3].
\n\t\t\tThis chapter has focus on the use of cellulose as the matrix in the production of nanocomposites. Cellulose has critical importance namely because is the most abundant and widespread biopolymer on Earth. Owing to its abundance and specific properties, it is important noted for the development of environmental friendly, biocompatible, and functional composites, quite apart from its traditional and massive use in papermaking and cotton textiles [4]. Additionally different types of cellulose are available for the preparation of nanocomposites, namely vegetable cellulose (VC), bacterial cellulose (BC) and nanofibrillated cellulose (NFC). Although sharing similar chemistry and molecular structure, the different kinds of cellulose show important differences in terms of morphology and mechanical behavior. For example, BC and NFC are composed of fibers with nanosized dimensions as compared to VC, which might impart new properties, and in some cases improvements to the ensuing nanocomposite materials [5].
\n\t\t\tThe association of cellulose with different fillers can bring benefits like improvement of properties (optical, mechanical, …) and delivering unique functions by their use [6]. Cellulose has been used as a soft matrix to accommodate inorganic fillers to produce composites that bring together the intrinsic functionalities of the fillers and the biointerfaces offered by cellulose fibers [2]. Among the wide range of available inorganic fillers, in this review metal nanoparticles (Au, Ag, and Cu, among others) will be considered. Metal NPs exhibit properties that differ from the bulk analogues due to size and surface effects, thus the properties of the final materials can be adjusted as a function of the size, shape, particle size distribution of the nanofillers as well as by interactions occurring with the cellulose fibers’ surfaces. Preparative strategies play a determinant role in the performance and properties of the nanocomposites, hence chemical approaches for the synthesis of these materials are reviewed namely for in situ and ex situ methods. Examples will be given for applications of cellulose nanocomposites by taking in consideration the type of nanoparticles used. As a concluding note, the development of new multifunctional cellulose nanocomposites will be put in perspective.
\n\t\tThe last years have seen great interest in research and application of cellulose nanocomposites namely due to the technological interest in renewable materials and environmentally friendly and sustainable resources [7]. In fact, within the polymers obtained from renewable sources, cellulose is the most abundant natural polymer in Nature as well as the most important component of the plants’"skeleton". This biopolymer formed by repeated connection of glucose building blocks is the structural basis of cell walls of virtually all plants and is usually considered an almost inexhaustible source of raw materials [8, 9]. Cellulose has particular significance owing its unique structure and distinct tendency to form intra- and inter-molecular bonding. These characteristics influence the cellulose supramolecul ararrangement that together with other practical aspects such as the product origin and processing treatment, have important consequences on the final properties of cellulose. This polymer is the main constituent of softwood and hardwood, representing about 40-45% of dry wood, with wood pulp remaining the most important source for cellulose processing namely in paper fabrication [8, 10, 11]. Wood pulp is also the main industrial feedstock for the production of cellulose regenerate fibers and films. This biopolymer is also used in the synthesis of different cellulose derivatives such as esters and ethers. These derivatives are well-kwon active components in applications which include coatings, pharmaceutics and cosmetics, among others [11] and also used in numerous hybrids containing metal and metal oxides NPs.
\n\t\t\tBesides extraction from plants, cellulose can be produced by alternative methods, namely by using different types of microorganisms (certain bacteria, algae or fungi). Among the cellulose-forming bacteria, Acetobacter strains have been widely used because they are not pathogenic. In fact, these Gram-negative bacteria are usually found in fruits and can be used in laboratorial conditions in order to obtain significant amounts of cellulose [8, 11-13]. Nowadays, it is observed a growing interest in the use of BC, not only within applications in nanocomposites but also in other fields including food industry (e.g. calorie–free dessert) and medical field (e.g. wound dressing). Apart their three-dimensional (3D) network of nanofibers, BC has high purity (do not have lignin, hemicelluloses, pectin and other compounds associated to VC), high degree of polymerization (DP up to 8000), high crystallinity (60 to 90%), high water content and high elasticity and mechanical stability (particularly in wet form) [8, 11-15].
\n\t\t\tChemical structure and morphological characteristicsof different forms of cellulose.
Due to the complex and expensive process to produce BC, there has been interest to find other ways to obtain cellulose fibers of nanometric dimensions, namely at an industrial scale [11]. NFC can be obtained from VC fibers by distinct methods including chemical treatment and mechanical disintegration procedures, in the form of aqueous suspensions of nanoscale fibers, leading to high aspect ratio materials (5-30 nm diameter and lengths in micrometer range) with remarkable strength and flexibility [16, 17]. The mechanical properties of NFC make this polymer a good candidate for reinforcement materials in nanocomposites. However, besides their interesting mechanical properties, NFC shows other properties of practical interest. For example, NFC has a large surface area which makes it a promising candidate for filtering membranes. Appropriate chemical modifications performed on NFC result in a versatile additive for paints, lacquers or latex. Due to its biocompatibility, NFC might also be used in food and medical applications [11, 17]. As will be clear in the next section, the properties of the cellulose nanocomposites depend not only on the NPs employed as fillers but also on the type of cellulose matrix used.
\n\t\t\tFrom all the cellulose derivatives commonly use on the chemistry market, esters and ethers are the predominant. Although produced since the middle of the eighteen century the actually research is related with their manufacture technological improvement. The mail goal is related with the development of greener processes being investigated the use of ionic liquids (IL), microwaves irradiation and solvent-free systems in the synthesis of this cellulose derivatives. This strategy has been followed for the cellulose derivatives used in specifics applications, such as biomedical and optoelectronic and produced in small amounts. The industries responsible for the production of high amounts of these derivatives (as cellulose acetate) have neglected this mandatory necessity [18].
\n\t\tA key aspect to consider in combining metal NPs with cellulose fibers is the methodology to be employed namely by taking in consideration the envisaged applications. In order to exploit the properties of nanocomposites, the NPs should be well dispersed over the matrix without the formation of large aggregates that may compromise the final properties and should as much as possible exhibit a small narrow size distribution. There is critical need to find effective techniques that allow the large-scale production that at the same time maintain control of the NPs dispersion in the cellulose matrix. A number of approaches have been developed to attach metal NPs onto cellulose fibers. Table 1 gives examples of methods employed in the preparation of cellulose/metal nanocomposites.
\n\t\t\t\tThe blending of inorganic NPs and polymers by promoting their homogeneous mixture to form nanocomposites materials has been widely employed [19]. Although this method offers the advantage of simplicity, the use of cellulose as matrix commonly lead to NPs aggregates that decrease the benefits associated to the presence of nanosized fillers. This process often leads to poor laundering durability of the materials and, for example when Ag NPs have been used, the antibacterial efficiency are lower than expected and discontinuous in time [20]. The direct deposition of Ag and Au NPs, by dropwise addition of the respective colloids onto filter papers, has been reported [21, 22]. Usually, this methodology does not lead to an homogeneous distribution of NPs on the paper substrates and the formation of aggregates at the edge of the droplets during the drying process is common [23].
\n\t\t\t\t\t\n\t\t\t\tThe preparation of cellulose/metal nanocomposites by the in situ reduction of metal salts in cellulose aqueous suspensions has been extensively investigated. Typically this involves the use of a soluble metal salt as precursor, a reducing agent and a co-stabilizer to avoid agglomeration. However, the in situ method can be employed without addition of an external reducing agent, because adsorption of metal ions on the cellulose surfaces may bet subsequently reduced to metal NPs by organic moieties such as terminal aldehyde or carboxylic groups, whose presence depend on pulp bleaching. In this case, the unique structure and the presence of ether and hydroxyl groups in cellulose fibers constitute an effective nanoreactor for in situ synthesis of the NPs. The ether and hydroxyl functions not only anchor the metal ions tightly onto the fibers via ion–dipole interactions, but also after reduction stabilizes the as prepared NPs via surface interactions [27, 57]. This process presents some advantages compared to the simple mixture of the composite components. The template role of the host macromolecular chains for the synthesis of NPs helps to improve their distribution inside the cellulose matrix and also prevents formation of aggregates. At the same time the polymer chains play an important role leading to a narrow size distribution and well defined shape for the metal NPs [69].
\n\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tCellulose matrix\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tPreparative method\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tMetal NPs\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t|
\n\t\t\t\t\t\t\t\t\tVegetable\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tBlending of components | \n\t\t\t\t\t\t\t\tAg [20, 21], Au [22] | \n\t\t\t\t\t\t\t|
\n\t\t\t\t\t\t\t\tIn situ reduction \n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tCellulose reducing groups | \n\t\t\t\t\t\t\t\tAg [24-29], Au [29, 30], Cu [31, 32], Pt [33, 34] | \n\t\t\t\t\t\t\t|
External reducing agents | \n\t\t\t\t\t\t\t\tAg [20, 27, 28, 35-38], Au [27, 36, 39, 40], Cu [31, 41, 42], Pt [27, 36, 43, 44], Co [45], Pd [27, 36] | \n\t\t\t\t\t\t\t||
UV reduction | \n\t\t\t\t\t\t\t\tAg [28, 46, 47] | \n\t\t\t\t\t\t\t||
Electrostatic assembly | \n\t\t\t\t\t\t\t\tAg [28, 36], Au [36, 39], Cu [48], Pt [36], Pd [36] | \n\t\t\t\t\t\t\t||
Microwave-assisted preparation | \n\t\t\t\t\t\t\t\tAg [49-51] | \n\t\t\t\t\t\t\t||
Surface pre-modification | \n\t\t\t\t\t\t\t\tAg [52], Au [52-54] | \n\t\t\t\t\t\t\t||
\n\t\t\t\t\t\t\t\t\tBacterial\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\tIn situ \n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tCellulose reducing groups | \n\t\t\t\t\t\t\t\tAg [55] | \n\t\t\t\t\t\t\t
Reducing agents | \n\t\t\t\t\t\t\t\tAg [19, 28, 37, 43, 56-60], Au [39, 43, 61-63], Cu [64], Pt [43, 65], Co [66] | \n\t\t\t\t\t\t\t||
Electrostatic assembly | \n\t\t\t\t\t\t\t\tAu [39] | \n\t\t\t\t\t\t\t||
UV reduction | \n\t\t\t\t\t\t\t\tAg [28] | \n\t\t\t\t\t\t\t||
Surface pre-modification | \n\t\t\t\t\t\t\t\tAg [67] | \n\t\t\t\t\t\t\t||
Diffusion | \n\t\t\t\t\t\t\t\tAg [28] | \n\t\t\t\t\t\t\t||
\n\t\t\t\t\t\t\t\t\tNanofibrillated\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tBlending of components | \n\t\t\t\t\t\t\t\tAg [68] | \n\t\t\t\t\t\t\t|
Electrostatic assembly | \n\t\t\t\t\t\t\t\tAg [16] | \n\t\t\t\t\t\t\t
Preparative methods of cellulose/metal nanocomposites.
The most commonly used in situ approach to prepare a dispersion of NPs in cellulose matrices involves the entrapment of metal cations in the fibers followed by their reduction with an external reducing agent. In this procedure the reducing agent also act as a co-stabilizer (together with the cellulose fibers) for the metal NPs. Sodium borohydride has been extensively used to reduce metal ions in cellulose matrices. The particle size distribution is adjusted by varying the NaBH4: metal salt molar ratio. The use of tri-sodium citrate has also been reported as reducing and stabilizing agent. Some reports have described the loading ofAg NPs into grafted filter paper [35], in BC and VC matrices [37].
\n\t\t\t\t\t\tThe use of hydrazine, hydroxylamine and ascorbic acid together with gelatin or polyvinylpyrrolidone (PVP) as colloidal stabilizers has been investigated [58]. Ascorbic acid acted as an efficient reductant for Ag+ and gelatin a good colloidal stabilizer toavoid NPs coalescence and to control particle size. In situ Ag ions reduction by the chelating-reducing agent triethanolamine (TEA) has been reported to produce small spherical particles with 8.5 nm average size, appearing well dispersed in the BC bulk ultrafine reticulated structure [59].
\n\t\t\t\t\t\tReduction of gold salts by flowing H2 over the cellulose matrix has been reported [40]. This methodology allows the preparation of NPs about 2 nm mean diameter. A facile one-step method, in aqueous medium, makes use of poly (ethyleneimine) (PEI) as reducing and macromolecular linker [61]. In this case the thickness of the Au coating surrounding the cellulose fibers can be adjusted by adding different halides (Fig. 2).
\n\t\t\t\t\t\tScheme illustrating the formation of Au–BC nanocomposites using the polyelectrolyte PEI (Adaptedby permission from ref [61] (Copyright 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim).
An alternative route for the in situ preparation of cellulose based nanocomposites involves the reducing groups of cellulose that simultaneously can entrap NPs within the fibers net. This process shows the advantage that external chemicals are not added to the reacting mixture, thus avoiding adventitious contaminations that may interfere in some applications such as catalysis [36].
\n\t\t\t\t\t\tThis methodology constitutes a green approach to the synthesis of a variety of metal NPs in cellulose matrices in which no additional reducing agents or colloidal stabilizers are used. Kunitake et al. [27] have reported pioneer research using VC fibers with following work reporting the use of BC fibers for the production of silver and gold nanostructures [28, 39]. This strategy has been reported for other types of biomaterials, hence Ag NPs have been prepared by using the in situ reduction of a silver(I) salt in the presence of cotton fibers. The washing durability of these nanocomposites and the small amounts of silver NPs required, make this an alternative path to produce cellulose based functional textiles. BC and porous cellulose have also been used as reducing and stabilizer for several metal NPs using a hydrothermal method [43, 55].
\n\t\t\t\t\t\tIn the context of composite science, ionic liquids have attracted substantial interest because of their ability to dissolve biopolymers like cellulose. This has been illustrated in the formation of cellulose/Au nanocomposites [30]. The combined use of cellulose and IL allowed the NPs morphology controlin a process in which the IL was retrieved after metal reduction.The use of unbleached kraft fibers have the advantage of limiting metal leaching due chemical affinity between the NPs and the substrate. In this case NPs are formed directly on the VC fiber surfaces by a redox reaction with the associated lignin. This has not been observed for fibers that do not contain lignin [29].
\n\t\t\t\t\tThe in situ reduction using UV irradiation is a simple method to produce metal NPs on the surface of cellulose fibers. The preparation of the nanocomposites is based on the photo-activation of cellulose surface by photons, followed by chemical reduction of metal salts. A possible mechanism is based on the number of reducing sites at the surface of cellulose fibers that are activated by UV photons [46]. The active role of reducing ends of cellulose chains in this mechanism has been demonstrated by employing cellulose fibers (VC and BC) in which such groups had been removed to show that metal NPs are not formed [28]. For cellulose/Ag nanocomposites [28, 46, 47] it was demonstrated the relevance of UV light intensity and time of irradiation as important parameters to control the amount of silver and their dispersion in the final composites. The metal NPs formed by this method tend to coat the cellulose fibers, with tendency to aggregate over prolonged times of UV irradiation, eventually leading to NPs with variable morphologies.
\n\t\t\t\t\tThe electrostatic assembly of NPs is based on the sequential adsorption of oppositely charged species on a solid substrate which very often is mediated by ionizable polymers [70]. This assembly technique offers some advantages over other methodologies due to the possibility of a better control of inorganic content in the final nanocomposites, full control of NPs size and morphology, and normally leads to less agglomeration of previously prepared NPs.
\n\t\t\t\t\tCellulose fibers dispersed in water are negatively charged over a wide pH range (2-10), due to the presence of ionizable moieties such as carboxyl and hydroxyl groups, resulting from chemical processing or from minor polysaccharides such as glucuronoxylans [71]. The deposition of Au NPs [39, 72] onto cellulosic fibers was achieved by previous treatment of fibers using multi-layers of poly (diallyldimethylammonium chloride) (polyDADMAC), poly (sodium 4-styrenesulfonate) (PSS), and again polyDADMAC. The use of a positively charged polyelectrolyte as the outer layer favored electrostatic interactions of the fibers with negatively surface charged Au NPs. This methodology has been also applied to the fabrication of Ag/NFC composites using distinct polyelectrolytes as macromolecular linkers [16]. Another example of an electrostatic assembly procedure was based on the chemical modification of cellulose with (2,3-epoxypropyl) trimethylammonium chloride (EPTAC) [36, 73]. This methodology allowed the grafting of the cellulose substrates with positive ammonium ions which is particularly useful for attachment of metal NPs with surface negatives charge.
\n\t\t\t\tChemical modification of cellulose can be performed to produce distinct types of cellulose/metal nanocomposites. In this context, common cellulose derivatives such as carboximetilcellulose, cellulose acetate and hydroxypropil cellulose have been used [74-76]. 2,2,6,6-tetramethylpyperidine-1-oxy radical (TEMPO) has been used to oxidize selectively the C6 primary hydroxyl groups of cellulose resulting in the corresponding polyuronic acids [67]. In this context, BC acts as an efficient template with the surface carboxylate groups used to quantitatively anchor metal ions via an ion-exchange reaction. The subsequent reduction of the cationsat the nanofibers’ surfaces originated metal NPs with a narrow size distribution. Chemical surface modification of hydroxyl groups into aminic groups, which act as selective coordination sites [52] and the use of thiol labeled cellulose through spontaneous chemisorption [53] has been demonstrated. In the latter, chemical attachment of the NPs onto the fibers’ surface limits particle desorption, hence extending the lifetime of the resulting hybrid materials.
\n\t\t\t\t\tThe fabrication of size-controlled metal nanowires using cellulose nanocrystals as biomolecular templates has been reported [54]. This method allowed designing Au nanowires of variable sizes that exhibit unique optical properties by controlling the thicknesses of gold shells. In another approach microwave irradiation was used as an efficient method to prepare cellulose/metal nanocomposites [49]. In this study cellulose was treated in a lithium chloride (LiCl)/ N,N-dimethylacetamide (DMAc) and ascorbic acid mixture to produce a homogeneous distribution of Ag NPs within the cellulose matrix. More recently the same group has reported the use of ethylene glycol as solvent, reducing reagent, and microwave absorber, thus excluding an additional reducing agent [50]. This one-step simultaneous formation of Ag NPs and precipitation of the cellulose is a suitable method due to its characteristics of rapid volumetric heating, high reaction rate, short reaction time, enhanced reaction selectivity, and energy saving [49, 77]. A similar methodology was applied in a one-pot process to produce Ag–cellulose nanocomposites, however in this case the cellulose matrix was used as the reducing and stabilizer agent in water suspensions [51].
\n\t\t\t\tThere are a variety of metal NPs that can be used as dispersed phases in bionanocomposites with cellulose. In the last decades there has been great progress in the colloidal synthesis of inorganic NPs. Colloidal metal NPs have received great attention due to their unique optical, electronic, magnetic, antimicrobial properties. Their small size, large specific surface area and tunable physico-chemical properties that differ significantly from the bulk analogues led to intense research on their use in composite materials [78]. This section gives examples of research on metal NPs used as fillers in cellulose nanocomposites. The applications of these materials are related with the type of NPs present though new properties arise due to the combined use of the metal NPs and cellulose. Table 2 summarizes important applications of cellulose/metal nanocomposites and a brief description will follow in this section.
\n\t\t\t\tNowadays a renewed interest in Ag antimicrobial materials has reappeared mainly due to the increase of multi-drug resistance of microbial strains to conventional antibiotics. The design of protective medical clothing or antibacterial packaging materials are examples of this current trend [35]. Ag NPs are well known by their strong cytotoxicity towards a broad range of microorganisms, such as bacteria and fungi [79].
\n\t\t\t\t\tSimilarly to other applications, well dispersed Ag NPs in the cellulose matrix are required otherwise the antimicrobial effect decreases. However, important parameters such as particle size distribution, metal content, cationic silver release and interaction with the surface of cellulose are also relevant parameters that influence the antimicrobial activity of these nanocomposites [23, 69]. Due to the high water holding capacity and biocompatibility, BC wound dressing materials with improved antimicrobial activity have been prepared using Ag [57, 60]. Other examples include the development of antibacterial food-packaging materials [35, 80], bactericidal paper for water treatment [20] and the study of laundering properties of nanocomposites [24, 81].
\n\t\t\t\t\t\n\t\t\t\t\tThe cellulose fibers can be chemically functionalized creating reactive sites in order to control the in situ synthesis of Ag NPs. Few examples are known of composites of NFC and metal NPs [16, 68]. Thus NFC functionalization with fluorescent Ag nanoclusters has been performed by dipping nanocellulose films into a colloid of Ag protected with poly(methacrylic acid) (PMAA) [64]. The electrostatic assembly of commercial Ag NPs onto NFC mediated by polyelectrolyte linkers have been described as a possible route to scale up the preparation of Ag/NFC composites [16].
\n\t\t\t\t\tNanostructured metals such Ag and Au are well known substrates for surface enhanced Raman scattering (SERS). Strong enhancement of the Raman signals is observed for certain molecules chemisorbed to the surface of these metals. Therefore the combined use of these metal NPs and cellulose is of great interest to develop molecular detection and biosensing platforms [37]. In this context, the use of cellulose nanocomposites might bring several advantages such as the fabrication of handy and low cost substrates in the form of paper products. A study on the use of distinct cellulosic matrices containing Ag NPs has shown that the BC/Ag nanocomposites were more sensitive as compared to the vegetable analogues, namely in biodetection of amino acids [37]. The use of filter paper with Ag NPs or Au NPs demonstrate the potential of these materials as SERS platforms to study diverse analytes such as p-hydroxybenzoic [21], single-walled carbon nanotubes [82] and binary mixtures of 9-aminoacridine-acridine and acridine-quinacrine separated by paper chromatography [83].
\n\t\t\t\t\tA simple and low-cost approach to the fabrication of fuel cells has been described based on a nanostructured Ag electrocatalyst and cellulose. Heat removal of the template and combination with graphite improved oxygen reduction in basic medium [38].
\n\t\t\t\t\n\t\t\t\t\t\t\t\t\tMetal NPs \n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tApplication\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tMetal NPs \n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tApplication\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t|
\n\t\t\t\t\t\t\t\t\tAg\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tAnti-counterfeiting | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\tAu \n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tBiosensors | \n\t\t\t\t\t\t\t|
Antimicrobial | \n\t\t\t\t\t\t\t\tArtificial skin | \n\t\t\t\t\t\t\t\tCatalytic | \n\t\t\t\t\t\t\t||
Food-packaging | \n\t\t\t\t\t\t\t\tConducting | \n\t\t\t\t\t\t\t|||
Water treatment | \n\t\t\t\t\t\t\t\tElectronic devices | \n\t\t\t\t\t\t\t|||
Wound dressing | \n\t\t\t\t\t\t\t\tMedical (Drug and protein delivery) | \n\t\t\t\t\t\t\t|||
Biosensors | \n\t\t\t\t\t\t\t\tSERS | \n\t\t\t\t\t\t\t|||
Catalytic | \n\t\t\t\t\t\t\t\tSmart papers and textiles | \n\t\t\t\t\t\t\t|||
Paper industry | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tCu\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tAntimicrobial | \n\t\t\t\t\t\t\t||
SERS | \n\t\t\t\t\t\t\t\tCatalytic | \n\t\t\t\t\t\t\t|||
Textiles | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tPd\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tCatalytic | \n\t\t\t\t\t\t\t||
\n\t\t\t\t\t\t\t\t\tPt\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tCatalytic | \n\t\t\t\t\t\t\t\tElectrocatalytic | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tCo\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\tElectronic actuators | \n\t\t\t\t\t\t\t
Photocatalytic | \n\t\t\t\t\t\t\t\tMagnetic | \n\t\t\t\t\t\t\t|||
Fuel cells | \n\t\t\t\t\t\t\t\tMicrofluidics devices | \n\t\t\t\t\t\t\t
Common applications of cellulose/metal nanocomposites.
The noble metal gold has long been a cornerstone precious metal occupying a premier position in the world economy, representing wealth and high value. Traditionally it has been used in its yellow lustrous bulk metallic form for monetary and jewelry applications and over recent decades as an electrical conductor and chemically inert contact material in the electronics industry [29]. Au NPs are among the most studied particles in modern materials science namely due to the number of available methods to produce colloids with uniformparticle sizes and well-defined morphologies. Stable Au NPs colloids have been prepared whose particles surfaces are efficiently stabilized by citrate anions in hydrosols or by alkanethiols when organic solvents are used [84].
\n\t\t\t\t\tCellulose/Au nanocomposites have been used as catalysts in glucose oxidation [40]. It has been reported that good dispersion of Au NPs in cellulose allowed effective contact with reactants making these materials good catalysts for the reduction of 4-nitrophenol. [85] Furthermore, cellulose can be used in several solvents having potential applicability in a variety of reactions. Another interesting possibility is the transformation of renewable biomass resources into valuable chemicals. Selective conversion of cellulose or cellobiose into gluconic acid catalyzed by polyoxometalate- [86] or CNT-supported by Au NPs [87] has been demonstrated. Agglomeration of the Au NPs in the cellulose nanocomposites has been described as a major limitation decreasing the catalytic activity of the composite materials.
\n\t\t\t\t\tCellulose based sensors have great interest in several applications including in fields as diverse as medical diagnosis, environmental control and food safety. It is important to develop materials that show good electron transfer capability, biocompatibility, stability and easy accessibility towards the analyte. Additionally large surface area for immobilization of the analytes, rapid response, high sensitivity, good reproducibility and anti-interference are also required characteristics. As expected, it is a great challenge to develop a single material that include all these important characteristics [63].
\n\t\t\t\t\tSEM images and micrographs (inset) of bacterial cellulose (BC) and derived composites: a) BC; b) BC/Ag; BC/Au and d) BC/Cu (bar: 1.5 µm).
Cellulose based sensors are inexpensive, disposable, and environmentally friendly. These materials transport liquids via capillary action with no need of external power [88]. BC/Au nanocomposites have been reported to exhibit good sensitivity, low detection limit and fast response toward hydrogen peroxide makingthese materials suitable matrices for enzyme immobilization [61-63]. The practical application of these nanocomposites for glucose biosensors in human blood samples has been reported. The values obtained showed good agreement with corresponding values obtained in hospital trials. The entrapment of Au NPs and enzymes in a paper coating material of sol–gel derived silica has been reported as a versatile material to be used as an entrapment medium and hydrophobic agent. This characteristic allowed more reproducible enzyme loading on rough and non-uniform paper surfaces [88].
\n\t\t\t\t\tConductive or semi-conductive nanocomposites containing Au NPs are very attractive for electronic applications. Although uniform NPs dispersions are required for many applications, for some cases controlled aggregation isused as an advantage. Electrical conductive cellulose films containing Au NPs have been prepared by self-assembly showing electrically conducting above a gold loading of 20 wt % [84]. The mechanism of electronic conduction in Au NPs-cellulose films is strongly dependent on the resistivity of the film [89].
\n\t\t\t\t\t\n\t\t\t\tCopper NPs were found to be good candidates as efficient catalysts in hydrogen production [90]. An important use for Cu NPs include the fabrication of low electrical resistance materials due to their remarkable conductive properties [91]. In addition Cu NPs and their oxides show broad spectrum biocide effects and the antimicrobial activity has been reported in studies of growth inhibition of bacteria, fungus, and algae [48].
\n\t\t\t\t\tAntimicrobial nanocoatings of Cu NPs on cellulose have been fabricated via electrostatic assembly [48]. In this process, a chemical pre-treatment step was performed in order to impart surface charge on the cotton substrate that promoted binding of cupric ions, followed by chemical reduction to yield metal nanostructured coatings. The resulting composites showed high effectiveness killing to multi-drug resistant pathogen A. baumannii. Compared to the Ag analogous there was no particle leaching for the copper nanocomposites.
\n\t\t\t\t\tThe use of microcrystalline cellulose as a porous natural material supporting copper ions has been demonstrated [31, 42]. Reducing agent and respective amount have critical importance to achieve Cu NPs (or the metal oxides) with controlled particle size. Conversion of CuO into Cu using cellulose as a reducing agent under alkaline hydrothermal conditions was described as a green process for the production of Cu at power low cost [32]. This process gives rise to the conversion of cellulose into value-added chemicals, such as lactic acid and acetic acid. The possibility of modifying the surface of cellulosic fibers and using chitosan has also been reported [41]. In this case, chitosan-attached cellulose fibers were used in the immobilization of Cu ions followed by a reduction step in the presence of borohydride to obtain Cu NPs. Unlike Au e Ag, non-coated Cu NPs oxidize extensively under ambient atmosphere. Although this detrimental effect is limited by incorporating the Cu NPs in bacterial cellulose, stable Cu/cellulose composites have been prepared by using Cu nanowires as inorganic fillers [64]. These nanocomposites are attractive for the emerging technologies based on electronic paper.
\n\t\t\t\tPlatinum is an useful material for numerous industrial catalytic applications and several reports have described the synthesis of Pt NPs using a variety of methods [33]. This metal is also considered the best electrocatalyst for the four-electron reduction of oxygen to water in acidic environments as it provides the lowest overpotential and the highest stability [65]. The preparation of Pt/cellulose nanocomposites generally involves the reduction of ionic Pt by addition of a reducing agent (NaBH4, HCHO, …) in the presence of cellulose, which might act as a structural-directing agent [43].
\n\t\t\t\t\tNanocomposites of Pt and amorphous carbon films were obtained by the catalyzed carbonization of cellulose fibers [44]. This type of NPs has been synthesized using NaBH4 as reducing agent in hydrothermal conditions in the presence of nanoporous cellulose [43]. The Pt NPs were well dispersed and stabilized in the cellulose network thus avoiding particle aggregation. Cationic cellulose bearing ammonium ions at the surface has also been used to produce this type of nanocomposites [36]. In this method, the attachment of negatively charged Pt NPs onto cationic cellulose substrates was promoted via electrostatic interactions, which result into high surface coverage of the fibers.
\n\t\t\t\t\tThermally stable proton-conducting membranes have been prepared by the in situ deposition of Pt NPs on BC membranes, via liquid phase chemical deoxidization method in the presence of the reducing agents NaBH4 or HCHO [65]. The obtained black nanocomposite have been reported to display high electrocatalytic activity, with good prospects to be explored as membranes in fuel cell field [63]. However in case of Pt/cellulose nanocomposites, the reducing groups of cellulose are less effective in the reduction of metal precursors. A supercritical CO2/ water system for reducing H2PtCl6 precursor to PtNPs using suspended crystalline cellulose nanofibrils of cotton has been described [33]. In this methodology VC was employedin a direct reduction route to form cellulose/Pt nanocomposites using a renewable reducing agent. The same authors have reported the use of cellulose nanocrystals (large surface area per unit weight in relation to normal cellulose fibers) for the same purpose. In this alternative the reaction temperature can be lowered to achieve Pt NPs with an average diameter of approximately 2 nm and with narrow particle size distribution [34].
\n\t\t\t\t\tThe incorporation of irregularly shaped Pt NPs dispersed in IL and cellulose acetate lead to a nanocomposite that exhibits synergistic effects in the activity and durability enhancement of the catalyst [92]. The authors have suggested that the presence of IL caused higher separation of the cellulose macromolecules which result in a higher flexible and lower viscous material. The ensuing nanocomposites displayed higher catalytic activity and stability when compared to the Pt NPs dispersed in the IL. Potential uses of cellulose/Pt nanocomposites in catalysis comprise the hydrogenation of cyclohexene [92] and hydrogen production [93].
\n\t\t\t\tCo NPs in cellulose matrices has been a topic of interest due to the potential application as magnetic nanocomposites. However, due to easy oxidation their use has been associated to the formation of metal alloys such as FeCo, as will be described in section 3.2.6. The properties of magnetic Co NPs are determined in large extent by surface atoms. In addition, crystallinity, size distribution, particles shape and neighboring particles, affect the response of the material when submitted to a magnetic field. Therefore the matrix in which the NPs are embedded, in this case cellulose, has strong influence on the magnetic properties of the NPs as well as the distance between them [45].
\n\t\t\t\t\tThe structure and morphology of Co NPs synthesized in cellulose matrix and resulting magnetic properties have been reported [45]. The authors have used two distinct chemical routes to investigate the effect on the structural properties of the NPs. In the borohydride reduction amorphous Co–B or Co oxide composites were obtained in which a detrimental effect on the magnetic properties was observed as compared to bulk Co. In contrast, using a NaH2PO2 reduction method, well-ordered ferromagnetic cobalt nanocrystals were obtained in which the magnetic properties of the samples resemble those of bulk cobalt.
\n\t\t\t\tThe properties of metallic systems can be significantly varied by blending the metal components into intermetallic compounds and alloys. The diversity of compositions, structures, and properties of metallic alloys not only can originate new properties but might also improve certain properties of the metal components due to synergistic effects [94]. The association of metal alloys (typically bimetallic) to cellulose yields interesting materials with well-defined, controllable properties and structures on the nanometer scale coupled with easier processing capability of the matrix. A tubular FeCo bimetallic nanostructure was obtained by using a cellulose/cobalt hexacyanoferrate (Fe–CN–Co) composite material as precursor [95]. The metal was then deposited onto a cellulose template via H2 gas-phase reduction that converted the precursor in FeCo bimetallic NPs. The FeCo NPs formed hollow tubular structures that mimic the original precursor composite morphology via a template-direct assisted method.
\n\t\t\t\t\tLightweight porous magnetic aerogels made of nanofibrils of VC and BC have been compressed into a stiff magnetic nanopaper [66]. The thick cellulose fibrils act as templates for the growth of discrete ferromagnetic cobalt ferrite NPs forming a dry, lightweight, porous and flexible magnetic aerogel with potential application in microfluidics devices and as electronic actuators. PdCu/BC nanocomposites showing high catalytic activity have been obtained, in which the PdCu NPs were homogeneously and densely precipitated at the surface [96]. Although the cost of these materials need to be considered, these compositesare of potential interest in water remediation processes because the Pd Cu alloy is considered the best catalyst for the denitrification of polluted water.
\n\t\t\t\tThe combination of cellulose with distinct metal NPs to design multifunctional nanocomposites is an interesting approach to extend the scope of these materials to several areas of applications. A fluorescent nanocomposite exhibiting antibacterial activity has been achieved through the functionalization of NFC with luminescent silver metal nanoclusters [68]. A novel type of supramolecular native cellulose nanofiber/nanocluster adduct was obtained by using poly(methacrylic acid) (PMMA) as the mediator between Ag nanocluster and cellulose. The PMMA not only stabilized the Ag nanoclusters but also allowed hydrogen bonding between the particles and cellulose. Another example reports Au and Ag NPs as colorfast colorants in cellulose materials for textiles with antimicrobial and catalytic properties [29].
\n\t\t\t\tAlso the combination of metal NPs with metal oxides is an emerging strategy to produce a range of multifunctional cellulose nanocomposites. The linkage of Ag NPs on magnetite containing BC substrates has been reported to produce magnetic and antimicrobial composites [97]. The possibility of bringing together diverse types of inorganics NPs and distinct cellulose matrices opens a new field for future applications, where the design of natural based multifunctional materials will be privileged.
\n\t\t\t\tMagnetic aerogels at different loadings of cobalt ferrite nanoparticles. SEM images of sample (a) 80 wt% of particles and sample (b) 95 wt% of particles (Scale bars, 4 µm). (c) HRTEM image of a single particle from sample (b) showing the lattice fringescorresponding to the {111} reflections of the spinel structure, and the corresponding distance. The image was fast Fourier transform (FFT) filtered for clarity.(d) Magnetic hysteresis loops of cobalt-ferrite-based aerogels. Inset: hysteresis loop of cobalt ferrite-based of sample (a) at T = 200 ºC. (Adapted by permission from Macmillan Publishers Ltd: Nature Nanotechnology([66]) (Copyright 2010).
The combination of metal nanoparticles and distinct types of cellulose matrices takes benefit of the properties of both components and simultaneously might result in properties due to synergistic effects. Besides the nature of the components in the final nanocomposite, the performance of the final material depends on the preparative methodologies employed in their production. This review has shown the relevance on the nanocomposite performance not only of the type of metal NPs used as fillers but also the origin of the cellulose matrix. In this context, methods that allow the chemical modification of both components, metal NPs and cellulose matrices, appear a very promising field of research to develop new functional materials. The combination of diverse metal NPs in cellulosic matrices is an important but less exploited strategy to prepare multifunctional composites. Fundamental studies concerning physico-chemical interactions that occur between the composite components have been scarce despite their obvious relevance in the optimization of the materials properties. Finally, the impact of these nanocomposites on health and environment is an issue in the agenda of the scientific community but whose importance will increase due to the commercialization of products based on these materials.
\n\t\tBC | \n\t\t\t\t\tBacterial cellulose | \n\t\t\t\t
CNT | \n\t\t\t\t\tCarbon nanotubes | \n\t\t\t\t
DMAc | \n\t\t\t\t\tN,N-dimethylacetamide | \n\t\t\t\t
DP | \n\t\t\t\t\tDegree of polymerization | \n\t\t\t\t
EPTAC | \n\t\t\t\t\t(2,3-epoxypropyl)trimethylammonium chloride | \n\t\t\t\t
FFT | \n\t\t\t\t\tFast Fourier transform | \n\t\t\t\t
HRTEM | \n\t\t\t\t\tHigh resolution transmission electron microscopy | \n\t\t\t\t
IL | \n\t\t\t\t\tIonic liquids | \n\t\t\t\t
NFC | \n\t\t\t\t\tNanofibrillated cellulose | \n\t\t\t\t
NPs | \n\t\t\t\t\tNanoparticles | \n\t\t\t\t
PEI | \n\t\t\t\t\tpoly(ethyleneimine) | \n\t\t\t\t
PMMA | \n\t\t\t\t\tpoly(methacrylic acid) | \n\t\t\t\t
polyDADMAC | \n\t\t\t\t\tpoly(diallyldimethylammonium chloride) | \n\t\t\t\t
PSS | \n\t\t\t\t\tpoly(sodium 4-styrenesulfonate) | \n\t\t\t\t
PVP | \n\t\t\t\t\tpolyvinylpyrrolidone | \n\t\t\t\t
SEM | \n\t\t\t\t\tScanning electron microscopy | \n\t\t\t\t
SERS | \n\t\t\t\t\tSurface enhanced Raman scattering | \n\t\t\t\t
TEA | \n\t\t\t\t\tTriethanolamine | \n\t\t\t\t
TEMPO | \n\t\t\t\t\t2,2,6,6-tetramethylpyperidine-1-oxy radical | \n\t\t\t\t
UV | \n\t\t\t\t\tUltraviolet | \n\t\t\t\t
VC | \n\t\t\t\t\tVegetable cellulose | \n\t\t\t\t
R.J.B. Pinto and M.C. Neves thank Fundação para a Ciência e Tecnologia (FCT) for the grants SFRH/BD/45364/2008 and SFRH/BPD/35046/2007, respectively. The authors acknowledge FCT (Pest-C/CTM/LA0011/2011), FSE and POPH for funding.
\n\t\tSoil formation is a complex process resulting from long-term interactions among several environmental factors, i.e., climate, soil-forming processes, and land uses [1]. Such processes influence soil’s physical, chemical, and biological characteristics and hence affect soil productivity [2]. In arid and semiarid regions, many challenges may face soil productivity; for example, many arid soils are of light texture with low organic matter and nutrient contents [3, 4, 5]. These soils exhibit low soil aggregation and can, therefore, be subjected easily to wind erosion [6]. Moreover, secondary minerals may dominate in such soils like calcite and gypsum [1], and these minerals can significantly diminish soil fertility [7, 8]. Another important threat that faces agricultural sustainability in arid sand semiarid soils is soil salinity [9]. Generally, the term arid or semiarid refers to the regions of limited rainfall and high evapotranspiration [10]. Areas with mean annual precipitation (MAP) ranging from 100 to 250 mm yr−1 are called arid climatic zones, while areas with MAP ranging between 250 and 600 mm yr−1 are called semiarid zones [11]. These two climatic regions cover approximately 30% or more of the total earth’s surface [12]. To improve the productivity of low-fertility soils, organic applications should therefore be incorporated within the top soil [13, 14] to raise soil contents of both C and nutrients [14]. However, the negative implications of using easily decomposed organic amendments on the environment should be taken into account, e.g., emissions of greenhouse that possesses global warming [15]. Accordingly, biochar might be the appropriate organic amendments to improve the characteristics of such soils but decrease the emissions of greenhouse gases on the other hand. In the following section, we will discuss the distribution of arid and semiarid soil and the potentialities of using biochar to improve soil properties and attain sustainability in crop production
As shown in Figure 1, arid and semiarid soils are located in North and South Africa, the Middle East region, North and South America, and finally in Australia [16]. More than 95% of the total arid soils exist in Africa and Middle East regions. According to the UNEP [16], aridity index (AI) is commonly used to quantify the aridity of a specific region. Briefly, this index is estimated based on climate variability by calculating the ratio of annual average rainfall to potential evapotranspiration (P/PET). For this concern, lands are classified in the following ascending order based on the average precipitation: hyperarid, arid, semiarid, and dry subhumid, and their average precipitation rates are 0, 1–59, 60–119, and 120–179 mm yr−1, respectively [16]. In this chapter we will focus on the Kingdom of Saudi Arabia lands as an example of arid lands and the major problems hindering the application of biochar technology in these soils. In the Kingdom of Saudi Arabia, almost 25% of the total land area is arable lands (52.7 million ha), in which 45% are calcareous, sandy textured soils, with very low contents of organic matter and nutrients [17].
Distribution pattern of arid and semiarid regions [16].
Salt content, in many arid soils, is relatively high. These soils accumulate on the soil’s surface because of the high evapotranspiration rates. In addition, these regions have dry climate with high temperature and high evaporation rate. The deeper soil layers are usually occupied by Ca. The arid soils can be applicable for cultivation in case proper water for irrigation becomes available. Due to high temperature, the degradation rate of soil’s organic matter in arid soils is very high; consequently, these soils need further application rates. In the Kingdom of Saudi Arabia, most of agricultural soils are of coarse texture, with high CaCO3 contents and high pH values. The lack of sufficient water in the Kingdom of Saudi Arabia led to increase the potentiality of soil salinization. Therefore, these soils are of poor fertility, in terms of physical (high infiltration rate, sand texture, and bad hydraulic properties), chemical (low organic matter contents, insufficient nutrients, and high soil pH), and biological (low microbial communities in soils due to the absence of organic residues and soil nutrients) characteristics [18]. Usually the pH value in the Kingdom of Saudi Arabia soils is greater than 8 with high CaCO3 contents (>30%) [19]. In spite of the Kingdom of Saudi Arabia having the largest land mass among Middle East countries, it has the lowest arable land per capita worldwide [20]. A point to note is that the major water sources in the Kingdom of Saudi Arabia are groundwater and desalination of seawater [21]. Therefore, intensive studies are performed to overcome the infertility problems of arid soils in the Kingdom of Saudi Arabia by using organic and inorganic soil amendments, i.e., compost bio inoculums and mineral polymers [22, 23, 24]. However, these amendments need to be applied intensively because of their low nutritive contents and fast degradation rates [25].
Due to the arid characteristics of Kingdom of Saudi Arabia lands, agricultural activities are also thought to be very low. According to the World Bank [20], the agricultural lands in the Kingdom of Saudi Arabia cover only 1736.472 km2 [20]. On the other hand, the Kingdom of Saudi Arabia is considered the largest food and agricultural importer in the Gulf Cooperation Council with average imported food products of 80% in 2013 [26, 27]. These conditions hinder the development of the agricultural sector in the Kingdom of Saudi Arabia. A positive point to note is that such arid conditions are suitable for cultivation of date palm plant. According to the Food and Agricultural Organization (FAO), the Kingdom of Saudi Arabia has the highest harvested areas of date palm in 2016 with an average area of 145,516 ha. Palm trees generate huge wastes annually [28]; accordingly, proper recycling and management of these wastes can improve soil conditions.
Biochar is an organic carbon-rich product, produced by burning agricultural and animal wastes in the absence of oxygen [29]. Several studies demonstrated its beneficial role for improving soil fertility and waste management, remediation of contaminated soils and water, and reducing greenhouse gas emissions [25, 30, 31]. In this chapter, we will discuss the potential benefits of biochar as a soil amendment for improving its fertility and productivity.
Biochar was initially produced by ancient Egyptians to produce liquid wood tar from charring processes in order to cover and preserve the dead bodies [32]. Thereafter, in South America (terra preta), 2500 years later, biochar is created both naturally by forest fires and by humans through burning bits for different practices, i.e., cooking and manufacturing [25]. In terra preta soils, the acidic conditions were the limiting factors affecting negatively crop production wherein these soils suffer severely from Al toxicity. To overcome this problem, the liming effect of biochar was an effective approach to overcome Al toxicity in soil [33].
All organic materials (feedstock, crop wastes, animal wastes manure) can be used for biochar production. Simply, biochar is a charcoal-like material that is produced in the absence of oxygen or limited oxygen conditions [25]. In this process organic wastes are burned at relatively low temperature < 700°C, and three main components are produced through the pyrolysis process, i.e., solid biochar (carbonized biomass with average C contents of >60), synthetic gas (which can be used as a power source), and bio oil (fuel material) [25]. Farmers in the past used to burn the agricultural wastes under limited oxygen conditions by covering the waste piles with soil dust. In this traditional method, approximately half the amount of organic C was lost into the atmosphere. Therefore, people have tried to develop the production technology through using pit kiln and brick kilns in order to eliminate the losses of C and other gas emission. After biochar technology has risen, non in situ equipment have been designed to maximize the biochar yield, eliminate the C lose and ash content and using syngas and bio oil as secondary products [25]. It is worthy to mention that organic materials start to decompose at low temperature (about 120°C), followed by hemicellulose and lignin compounds, which degrade at 200–260°C and 240–350°C, respectively [34].
Both pyrolysis conditions and the types of organic wastes identify the major characteristics of the produced biochar [25, 35]. Usually biochar (a carbon-rich product) is characterized by its high surface area and lower concentrations of hydrogen and oxygen [36, 37]. Thus, its application can improve soil characteristics (chemical, physical, and biological). Moreover, this organic product is considered relatively stable in soil because of its low availability of labile organic carbon [38] besides its low content of nutrients [39]. Table 1 shows the main physiochemical characteristics of different types of biochars. For both physical and chemical characteristics, pyrolysis conditions and type of organic wastes are the main factors identifying them. Clearly, all biochars have the same characteristics, especially the high C contents and low N contents. Nitrogen usually starts to be volatile at 200°C; therefore, N contents are low in most types of biochars. The high pH of biochar might be attributed to the high content of alkaline metals, i.e., Ca, Mg, and K, which are stable during biochar production. Despite the low nutrient content of biochar, its application to soils improves its fertility because it is usually added at high rates as soil amendments. The pyrolysis conditions play an important role for identifying the physical characteristics of biochar. The higher surface area of biochar is a consequence of high temperature during the pyrolysis reaction [25].
Feedstock | TemPerature | pH | % | CEC, cmolc kg−1 | C/N ratio | % | H/C ratio | O/C ratio | SSA, m2 g−1 | Reference | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
C | N | P | S | Ca | Mg | K | O.M | Ash | |||||||||
Sugar cane bagasse | <500 | 8.63 | 74.02 | 1.00 | 0.24 | — | 0.17 | 0.32 | 2.00 | 69.62 | 74.02 | 87.80 | 12.21 | 0.42 | 0.23 | 92.30 | [31] |
Orange peel | <500 | 8.75 | 66.36 | 2.13 | 0.25 | — | 1.04 | 0.28 | 1.86 | 68.28 | 31.15 | 88.80 | 11.17 | 0.65 | 0.32 | 0.20 | |
Oak wood | 600.00 | 6.38 | 87.50 | 0.20 | — | — | — | — | — | 75.70 | 489.00 | — | 0.01 | 0.33 | 0.07 | 642.00 | [40] |
Corn stover | 350.00 | 9.39 | 60.40 | 1.20 | — | — | — | — | — | 419.30 | 51.00 | — | 11.40 | 0.75 | 0.29 | 293.00 | [41] |
600.00 | 9.42 | 70.60 | 1.07 | — | — | — | — | — | 252.10 | 66.00 | — | 16.70 | 0.39 | 0.10 | 527.00 | ||
Corn stalk | 400.00 | 9.60 | 51.10 | 1.34 | 0.25 | — | — | — | 1.34 | — | 38.13 | — | — | — | — | — | [42] |
500.00 | 10.10 | 48.40 | 0.55 | 0.44 | — | — | — | 2.65 | — | 88.00 | — | — | — | — | — | ||
Wheat straw | 425.00 | 10.40 | 46.70 | 0.59 | — | — | 1.00 | 0.60 | 2.60 | — | 79.15 | — | 20.80 | — | — | — | [43] |
Rice straw | 400.00 | — | 71.30 | 1.46 | — | — | — | — | 24.60 | — | 48.84 | — | 36.20 | — | — | — | [44] |
Peanut hull | 500.00 | 8.60 | 82.00 | 2.70 | 0.30 | 0.10 | — | — | — | — | 30.37 | — | 9.30 | 0.44 | 0.03 | 200.00 | [45] |
Coco peat | 500.00 | 10.30 | 84.40 | 1.02 | 0.03 | 0.27 | 0.06 | 2.30 | — | — | 82.75 | — | 15.90 | 0.41 | 0.10 | 13.70 | [46] |
Coconut charcoal | <500 | 8.86 | 76.50 | 0.20 | — | — | — | — | — | — | 426.60 | — | 2.90 | 0.12 | — | — | [47] |
Pinewood | <500 | 8.47 | 53.20 | 0.40 | — | — | — | — | — | — | 143.40 | — | 65.70 | 0.35 | — | — | |
Eucalyptus deglupta | 350.00 | 7.00 | 82.40 | 0.57 | 0.06 | 0.03 | — | — | — | 4.69 | 144.56 | — | 0.20 | — | 0.12 | [48] | |
Hardwood sawdust | 500.00 | — | 63.80 | 0.22 | — | 0.01 | — | — | — | 290.00 | — | 22.80 | 0.60 | 0.14 | 1.00 | [49] | |
Chinese pine | 600.00 | 8.38 | 66.67 | 2.21 | — | — | — | — | — | 31.58 | 30.17 | — | 12.50 | 0.58 | 0.31 | — | [50] |
Cattle waste | 380.00 | 8.20 | 62.10 | 0.10 | — | — | — | — | — | 39.00 | 621.00 | — | 25.60 | 1.90 | 0.27 | — | [51] |
Sewage sludge | 380.00 | 8.50 | 38.30 | 5.20 | — | — | — | — | — | 0.50 | 7.37 | — | 44.90 | 0.94 | 0.25 | — |
Physicochemical characteristics of different types of biochar.
Data obtained from Abdelhafez et al. [25].
As mentioned above the porous structure of biochar facilitates its adsorption of water and, therefore, increases soil water holding capacity [52, 53]. This might increase the efficiency of water use in the arid zone soils [54]. The previous studies also demonstrated that the addition of biochar increases both soil aggregation and saturated hydraulic conductivity but decreases soil bulk density [53, 55, 56]. Therefore, application of biochar is a recommended practice to improve the physical characteristics of light textured soils [3]. For soil chemical characteristics, most studies showed that biochar has a negative effect on the availability of soil nutrients, i.e., its application increases soil pH [57, 58]. The liming effect of biochar can be attributed to the high concentrations of cationic metals, i.e., Ca2+, Mg2+, and K+, which are stable and do not volatilize during the pyrolysis process [25]. In most cases, biochar has a relative high pH (within the range of 8–11.5) [57, 59, 60]. Therefore, addition of biochar is more favorable for acidic soils than the alkaline ones. The black earth (terra preta) was an acidic soil in the enteral Amazon basin, and AL toxicity and P deficiency were the main reasons hindering the agricultural activities. Continuous applications of biochar to these soils neutralized soil acidity but increased the available P fraction; consequently, biochar enhanced and sustained soil health of terra preta [25, 32, 59]. Moreover, high doses of biochar can increase soil salinity [61, 62, 63, 64, 65]. On the other hand, the addition of biochar can raise soil organic matter contents and elevate soil cation exchange capacity (CEC) [66]. For nutrients contents, it is worth mentioning that most biochar types are typically low in nutrient contents, especially N. As a result, applications of biochar only in agricultural is not adequate to supply the needed macro- and micronutrients [25, 67]. However, biochar plays an important role in mitigating soil nutrient losses by seepage or leaching [66]. Applications of biochar to soils increased its OC contents, which is suitable for soil organisms and provides more favorable habitats to microbes and, therefore, facilitates soil biological activities [68]. In addition, the release of organic molecules suppresses the activities of soil microbes [69].
As mentioned above the high pH of biochar limited its applications in arid soils. For this concern, application of biochar to agricultural soils in the Kingdom of Saudi Arabia is very limited due to many reasons as follows:
Low cultivated areas in the Kingdom of Saudi Arabia: as mentioned above, agricultural activities in the Kingdom of Saudi Arabia are very limited due to the arid conditions.
The chemical characteristics of soils in the Kingdom of Saudi Arabia; especially soil pH is one of the major factors hindering the application of biochar to agricultural soils. Our demonstration proves that most types of biochar are of alkaline nature and its application to agricultural soil may negatively affect the availability of soil nutrients due to increasing soil pH. The pH of the produced biochar is a function of pyrolysis temperature and time; by elevating the pyrolysis temperature and time, the pH of the produced biochars increased to reach 11.5 in some studies [53].
The lack of knowledge regarding biochar technology and its beneficial role for enhancing agricultural activates.
In a bibliometric study conducted by Arfaoui et al. [70], they have shown that Iran, the Kingdom of Saudi Arabia, and Egypt are the highest contributor countries for biochar studies and publications in the Middle East countries. As shown in Figure 2 (biochar article number and geographic distribution according to the lead author’s country of origin), China, the USA, and Iran are the leader countries for biochar studies and publications, followed by Pakistan, Middle East countries (Egypt and the Kingdom of Saudi Arabia), and to a lesser extent in Australia. In the Kingdom of Saudi Arabia, the Saudi Biochar Research Group in the King Saud University (Saudi Arabia) contributed to most publications in the Middle East countries.
Article number and geographic distribution according to the lead author’s country of origin [70].
We concluded that biochar is a promising soil amendment that can be used effectively for enhancing soil fertility. In arid regions like the Kingdom of Saudi Arabia, additional researches are needed to investigate the potential neutralization of biochar alkalinity; consequently, it can be added safely to agricultural soils. There are different sources of agricultural and food wastes that can be used for biochar production. In the case of date palm wastes, the average annual waste of one tree is about 40 kg; therefore, date palm wastes can be used effectively for biochar production in the Kingdom of Saudi Arabia. Therefore, the government of Kingdom of Saudi Arabia has to encourage the scientists for initiating intensive researches on biochar production and investigate its beneficial roles for improving soil fertility and agricultural production.
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",metaTitle:"Edited Volumes",metaDescription:"The Edited Volume, also known as the InTechOpen Book, is an InTechOpen pioneered publishing product. Edited Volumes make up the core of our business - and as pioneers and developers of this Open Access book publishing format, we have helped change the way scholars and scientists publish their scientific papers - as scientific chapters. ",metaKeywords:null,canonicalURL:"/pages/edited-volumes",contentRaw:'[{"type":"htmlEditorComponent","content":"WHY PUBLISH IN AN INTECHOPEN EDITED VOLUME?
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\n\nOut of all of the publishing options available to researchers, why choose to contribute your research to an IntechOpen Edited Volume? The reasons are simple. IntechOpen has worked exceptionally hard over the past years to fine tune the Open Access book publishing process and we continue to work hard to deliver the best for all of our contributors. The quality of published content is of utmost importance to us, followed closely by speed, and of course, availability and accessibility. To view current Open Access book projects that are Open for Submissions visit us here.
\n\nQUALITY CONTENT
\n\nOver the years we have learned what is important. What makes a difference to the researchers that work with us, what they value. Something that is very high not only on their lists, but our own, is the quality of the published content.
\n\nOur books contain scientific content written by two Nobel Prize winners, two Breakthrough Prize winners and 73 authors who are in the top 1% Most Cited.
\n\nWith regular submission for coverage in the single most important database, the Book Citation Index in the Web of Science™ Core Collection (BKCI), and no rejected submissions to date, over 43% of all Open Access books indexed in the BKCI are IntechOpen published books.
\n\nIn addition to BKCI, IntechOpen covers a number of important discipline specific databases as well, such as Thomson Reuters’ BIOSIS Previews.
\n\nACCESS
\n\nThe need for up to date information available at the click of a mouse is one thing that sets IntechOpen apart. By developing our own technologies in order to streamline the publishing process, we are able to minimize the amount of time from initial submission of a manuscript to its final publication date, without compromising the rigor of the editorial and peer review process. This means that the research published stays relevant, and in this fast paced world, this is very important.
\n\nYOUR WORK, YOUR COPYRIGHT
\n\nThe utilization of CC licenses allow researchers to retain copyright to their work. Researchers are free to use, adapt and share all content they publish with us. You will never have to pay permission fees to reuse a part of an experiment that you worked so hard to complete and are free to build upon your own research and the research of others. The Edited Volume helps bring together research from all over the world and compiles that research into one book - accessible for all. The research presented in chapter one can inspire the author of chapter three to take his or her research to the next level. It is about sharing ideas, insights and knowledge.
\n\nCan collaboration be inspired by a publishing format? At IntechOpen, the answer is yes. The way the research is published, the way it is accessed, it’s all part of our mission to help academics make a greater impact by giving readers free access to all published work.
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\n\nSee a complete overview of all publishing process steps and descriptions here.
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I am also a member of the team in charge for the supervision of Ph.D. students in the fields of development of silicon based planar waveguide sensor devices, study of inelastic electron tunnelling in planar tunnelling nanostructures for sensing applications and development of organotellurium(IV) compounds for semiconductor applications. I am a specialist in data analysis techniques and nanosurface structure. 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Here he worked as a robotic researcher with the university's Intelligent Manufacturing Systems Group as well as a guest researcher at various European universities, including the Swiss Federal Institute of Technology Lausanne (EPFL). During this time he published more than 20 scientific papers, gave presentations, served as a reviewer for major robotic journals and conferences and most importantly he co-founded and built the International Journal of Advanced Robotic Systems- world's first Open Access journal in the field of robotics. Starting this journal was a pivotal point in his career, since it was a pathway to founding IntechOpen - Open Access publisher focused on addressing academic researchers needs. Alex is a personification of IntechOpen key values being trusted, open and entrepreneurial. Today his focus is on defining the growth and development strategy for the company.",institutionString:null,institution:{name:"TU Wien",country:{name:"Austria"}}},{id:"19816",title:"Prof.",name:"Alexander",middleName:null,surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/19816/images/1607_n.jpg",biography:"Alexander I. Kokorin: born: 1947, Moscow; DSc., PhD; Principal Research Fellow (Research Professor) of Department of Kinetics and Catalysis, N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow.\r\nArea of research interests: physical chemistry of complex-organized molecular and nanosized systems, including polymer-metal complexes; the surface of doped oxide semiconductors. He is an expert in structural, absorptive, catalytic and photocatalytic properties, in structural organization and dynamic features of ionic liquids, in magnetic interactions between paramagnetic centers. The author or co-author of 3 books, over 200 articles and reviews in scientific journals and books. He is an actual member of the International EPR/ESR Society, European Society on Quantum Solar Energy Conversion, Moscow House of Scientists, of the Board of Moscow Physical Society.",institutionString:null,institution:{name:"Semenov Institute of Chemical Physics",country:{name:"Russia"}}},{id:"62389",title:"PhD.",name:"Ali Demir",middleName:null,surname:"Sezer",slug:"ali-demir-sezer",fullName:"Ali Demir Sezer",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/62389/images/3413_n.jpg",biography:"Dr. Ali Demir Sezer has a Ph.D. from Pharmaceutical Biotechnology at the Faculty of Pharmacy, University of Marmara (Turkey). 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I had been a visiting research student at Faculty of Computer Science, University of Murcia, Murcia, Spain for three months.\n\nI have published over 40 papers during 5 years in refereed journals, books, and conference proceedings in the areas of electro-physiological signals processing and classification, notably EMG and EOG signals, fractal analysis, wavelet analysis, texture analysis, feature extraction and machine learning algorithms, and assistive and rehabilitative devices. I have several computer programming language certificates, i.e. Sun Certified Programmer for the Java 2 Platform 1.4 (SCJP), Microsoft Certified Professional Developer, Web Developer (MCPD), Microsoft Certified Technology Specialist, .NET Framework 2.0 Web (MCTS). I am a Reviewer for several refereed journals and international conferences, such as IEEE Transactions on Biomedical Engineering, IEEE Transactions on Industrial Electronics, Optic Letters, Measurement Science Review, and also a member of the International Advisory Committee for 2012 IEEE Business Engineering and Industrial Applications and 2012 IEEE Symposium on Business, Engineering and Industrial Applications.",institutionString:null,institution:{name:"Joseph Fourier University",country:{name:"France"}}},{id:"55578",title:"Dr.",name:"Antonio",middleName:null,surname:"Jurado-Navas",slug:"antonio-jurado-navas",fullName:"Antonio Jurado-Navas",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/55578/images/4574_n.png",biography:"Antonio Jurado-Navas received the M.S. degree (2002) and the Ph.D. degree (2009) in Telecommunication Engineering, both from the University of Málaga (Spain). He first worked as a consultant at Vodafone-Spain. From 2004 to 2011, he was a Research Assistant with the Communications Engineering Department at the University of Málaga. In 2011, he became an Assistant Professor in the same department. From 2012 to 2015, he was with Ericsson Spain, where he was working on geo-location\ntools for third generation mobile networks. Since 2015, he is a Marie-Curie fellow at the Denmark Technical University. 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