Synthesis of TiO2 NPs by using plant extracts.
\r\n\tThe aim of this book will be to describe the most common forms of dermatitis putting emphasis on the pathophysiology, clinical appearance and diagnostic of each disease. We also will aim to describe the therapeutic management and new therapeutic approaches of each condition that are currently being studied and are supposed to be used in the near future.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"278931ae110500350d8b64805c70f193",bookSignature:"Dr. Eleni Papakonstantinou",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/7934.jpg",keywords:"Atopic eczema, Interleukin, Topical corticosteroids, Hand eczema, Blisters, Pruritus, Irritant contact dermatitis, Allergic contact dermatitis, Discoid eczema, Sebaceous glands, Inflammatory dermatitis, Facial rash",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"February 5th 2019",dateEndSecondStepPublish:"March 19th 2019",dateEndThirdStepPublish:"May 18th 2019",dateEndFourthStepPublish:"August 6th 2019",dateEndFifthStepPublish:"October 5th 2019",remainingDaysToSecondStep:"2 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"203520",title:"Dr.",name:"Eleni",middleName:null,surname:"Papakonstantinou",slug:"eleni-papakonstantinou",fullName:"Eleni Papakonstantinou",profilePictureURL:"https://mts.intechopen.com/storage/users/203520/images/system/203520.jpg",biography:"Dr. med. Eleni Papakonstantinou is a Doctor of Medicine graduate and board certified Dermatologist-Venereologist. She studied medicine at the Aristotle University of Thessaloniki, in Greece and she continued with her dermatology specialty in Germany (2012-2017) at the University of Magdeburg and Hannover Medical School, where she completed her dissertation in 2016 with research work on atopic dermatitis in children. During this time she gained wide experience in the whole dermatological field with special focus on the diagnosis and treatment of chronic inflammatory skin diseases and also the prevention and treatment of melanocytic and non-melanocytic skin tumors. Her research interests were beside atopic dermatitis and pruritus also the pathophysiology of blistering dermatoses. In addition to lectures at german and international congresses, she has published several articles in german and international journals and her work has been awarded with various prizes (poster prize of the German Dermatological Society for the project: 'Bullous pemphigoid and comorbidities' (DDG Leipzig 2016), 'Michael Hornstein Memorial Scholarship' (EADV Athens 2016), travel grant (EAACI Vienna 2016). Since 2017, she works as a specialist dermatologist in private practice in Dortmund, in Germany. Parallel she co-administrates an international dermatologic network, Wikiderm International and she writes a dermatology public guide for patients, as she is convinced that evidence-based knowledge has to be shared not only with colleagues but also with patients.",institutionString:"Private Practice, Dermatology and Venereology",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:null}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"270941",firstName:"Sandra",lastName:"Maljavac",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/270941/images/7824_n.jpg",email:"sandra.m@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, copyediting 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. 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This technique has the tendency to convert light energy into chemical energy under mild reaction conditions [1]. Subsequently, the technology has had successful application in many areas and is seen as a possible solution to the ever-increasing environmental and energy shortage issues.
Recent advancement in population growth coupled with the expansion of industrialisation has brought about serious environmental pollution and energy shortages. This has necessitated the rising demands for environmental remediation, the alternative supply of energy and novel methods for pollution eradication by researchers [2]. A lot of methods have been employed to degrade complex toxic pollutants to less toxic compounds. Among them are the convention ones (coagulation, oxidation, ion exchange, membrane filtration and flocculation) [2]. These methods are, however, considered ineffective by a lot of researchers due to their severe disadvantages including producing a large volume of sludge and operating at a very high cost [3]. Photocatalysis using semiconductors has been recommended as a potential method for environmental clean-up because it is economical and degrades pollutants by using artificial or natural sunlight which is cheap and abundant worldwide. Besides, there is no formation of sludge, and the catalyst can be reused after the process since it remains unchanged [4].
A number of semiconductors (TiO2, ZnO, Fe2O3, CdS and ZnO) have been employed for varied photocatalytic activities due to their unique properties such as excellent electronic structure and light absorption, degradation of pollutants, thermal stability, less toxicity, low cost and inertness [5]. However, these semiconductors suffer two serious drawbacks. These drawbacks include large energy band gap which is too wide to absorbed visible light [6]. Thus, these semiconductors are only photoactive in UV range. The second limitation is the rate at which the photo-generated electrons and holes recombine; a phenomenon that reduces the effectiveness of photodegradation process [7]. Hence, for a semiconductor to attain its maximum potential as an efficient photocatalyst, some effective modifications that can enhance its photosensitivity in the visible light range and also retard the recombination of the electrons and holes [8] are required. Thus, the development of a novel photocatalyst that has potential to eliminate the environmental pollutants is an essential requirement for photocatalysis process.
Documented reports on bismuth-related nanoparticles including BiOCOOH, Bi2WO6, (BiO)2CO3, BiVO4, BiPO4, Bi2O3 and BiOCl [9], have been found to attract considerable attention because of their proficient photocatalytic performance, cost-effectiveness, low toxicity and high stability. Modification of bismuth-related nanoparticles with metals and non-metal, carbonaceous materials and biopolymers is reported to further endow these catalysts with exceptionally high visible light responsivity and efficient photocatalytic performances [10]. Modified bismuth-related nanoparticles have been efficaciously utilised in many photocatalytic processes including antifogging, self-cleaning, disinfection, carbon dioxide reduction, organic pollutant degradation in water, hydrogen generation, air purification and so on.
This chapter discusses bismuth as a metal and its related nanoparticles. It also dwells on the modification of bismuth-based nanoparticles for enhanced photocatalytic activity and finally elaborated on the various photocatalytic applications/processes that these nanoparticles have been successfully applied to.
Bismuth (Bi) occurs naturally as a diamagnetic element with atomic number 83. It is a pentavalent transition metal and its oxides and sulphides represent significant commercial ore. It has low thermal conductivity, high Hall coefficient and high electrical resistivity [11]. Deposition of a thin layer of bismuth on the surfaces of materials causes it to behave as a semiconductor [12]. Again, bismuth is reported to be denser in its liquid phase than the solid phase and expands about 3% during solidification. This property enables it to be used as a component of alloys so that it can compensate for the contraction of other components of the alloy [12]. Bismuth is relatively non-toxic and has a relatively low melting point (271 C). Approximately, 63% bismuth is used to produce cosmetics, pigments and pharmaceuticals. 26% of it is also used in the field of metallurgy for galvanising and casting [13]. 7% is used in bismuth alloys, solders and ammunition and the 4% also are used in research fields [13].
The use of bismuth-based nanoparticles instead of the traditional bismuth-containing bulk materials/compounds for application in various advanced technological areas has received greater attention recently. This widespread interest in bismuth-based nanoparticles is as a result of the fact that the nanoparticles possess peculiar properties that are absent in the bulk solid materials. These unique features which include high optical, electrical, thermal, photocatalytic and magnetic properties are mainly dependent on the nanoparticles’ large specific surface area and small sizes [14]. Fortunately, opportunities exist, through colloidal chemistry, to synthesis bismuth-based nanoparticles. This process involves utilisation of bismuth salts as precursors with the addition of surface modifiers and reducing agents to produce size controllable and highly crystalline bismuth-based nanoparticles. Among the bismuth-based nanoparticles of interest are Bismuth chalcogenides, Bismuth vanadate, Bismuth oxyhalides and other bismuth-related nanoparticles.
Bismuth chalcogenides are a class of photoelectric compounds consisting of bismuth and group VI elements. These compounds are generally represented as Bi2E3 (E = O, S, Se, Te) and consist of bismuth oxide (Bi2O3), bismuth sulphide (Bi2S3), bismuth selenide (Bi2Se3) and bismuth telluride (Bi2T3). These class of compounds are technologically important semiconductors owing to their peculiar properties and have been applied in different industries. A recent study in bismuth chalcogenides’ visible-light-responsive properties and enhanced photocatalytic activities has stimulated a great research interest in their nanomaterials.
Bi2O3 is a p-type semiconductor with six crystallographic polymorphs which are represented as α-, β-, γ-, ω-, ε-, and δ-Bi2O3. Monoclinic α-Bi2O3 is the phase present at room temperature. This phase can transition to the face-centred cubic δ-Bi2O3 phase when heated. The other phases of Bi2O3 include tetragonal β-Bi2 phase, body-centred cubic γ- Bi2O3, orthorhombic ε-Bi2O3 and triclinic ω- Bi2O3 phases [15]. Bi2O3 has high refractive index, narrow energy band gap (2.40–2.80), dielectric permittivity and outstanding photoconductivity [16]. Bi2O3 is also considered as an amphoteric semiconductor as there are reports of the material exhibiting both p and n-type conductivity based on the methods of synthesis [16]. These properties enable Bi2O3 to be used as a sensor and electrochromic materials, optical coating and photocatalyst.
Bi2S3 possesses interesting optical and electronic properties and a direct band gap ranging from 1.3 to 1.7 eV. These qualities enable Bi2S3 to be applied in various fields including thermoelectric transport for the fabrication of optoelectronic, photovoltaic and thermoelectric devices [17] and photocatalysis. Various morphologies of Bi2S3 have been fabricated through different routes of synthesis. These one-dimensional nanostructures which include nanowires, nanotubes, nanorods and nanoflowers are considered to be the most appropriate for the above-named applications of Bi2S3 because of quantum confinement effect which subsequently enhances the thermoelectric efficiencies of the materials [18].
Bi2Se3 has a stacked layered laminated structure. Each layer is about 0.96 nm thick and contains five atoms which are bonded covalently along the z-axis in the following order: Se-Bi-Se-Bi-Se [19] (Figure 1). As a result of the weak interlayer forces of attraction, exfoliation of Bi2Se3 into few-layer nanosheets is possible [19]. Being a narrow band gap semiconductor (0.3 eV) with a high charge carrier mobility, Bi2Se3 has high potential application in photoelectrochemical and thermoelectrical devices as well as optical recording systems and photocatalysis [20].
Structure of bismuth selenide [21].
Bismuth telluride (Bi2Te3), is a semiconductor with a band gap of 0.15 eV. It has a trigonal structure and a high melting point of 585°C. When alloyed with antimony or selenium, Bi2Te3 becomes a highly efficient thermoelectric material at room temperature [21]. Because of these interesting properties, Bi2Te3 has been applied in thermoelectric power generation and refrigeration [22, 23].
Bismuth vanadate (BiVO4) exists in three main phases. These phases include tetragonal scheelite, monoclinic scheelite and tetragonal zircon. The monoclinic phase has high visible light activity due to the narrow nature of its band gap (2.4 eV) [24]. This visible light absorption behaviour has stimulated a lot of research investigation into its application in environmental remediation through photocatalysis. Again, BiVO4 has advantages over lots of its related semiconductors such as being environmentally friendly, highly resistant to photocorrosion, non-toxic and low cost [24].
BiOX, with the X representing either Br, Cl or I, are layered semiconductor materials that are crystallised in a tetragonal matlockite form [25]. The layered structure is arranged in such a way that each bismuth atom is encircled by four oxygen and halogen atoms resulting in an asymmetric tetrahedral symmetry (X-Bi-O-Bi-X) [25]. This arrangement enables BiOX to possess remarkable optical, mechanical, electrical and catalytic properties. As a result, BiOX has been utilised in selective oxidation of alcohols, organic synthesis, water splitting, indoor-gas purification and photodegradation of organic pollutants in wastewater [26].
Bismuth oxychloride (BiOCl), a p-type semiconductor, exhibits excellent ionic conduction, optical, catalytic and electrical properties. It is made up of chlorine ions (Cl−), bismuth ions (Bi3+) and oxygen ions (O2−) that pile up in tetragonal layered [Cl-Bi-O-Bi-Cl]n structure forming non-bonding attractions via the chlorine atoms (Cl) along C-axis. The four Bi-Cl and four Bi-O are arranged opposite to one another in a tetragonal pyramidal phase with the Bi in the centre of the structure (Figure 2). BiOCl is active in UV range with experimental band gap range of 3.1 to 3.5 eV while the theoretical values range from 2.8 to 2.9 eV [27].
Structure of bismuth oxychloride [27].
Bismuth oxybromide (BiOBr) nanoparticle is also a p-type semiconductor and a promising photocatalyst due to its excellent optical properties, chemical stability and effective photocatalytic activity. Its layered tetragonal structure and appropriate indirect band gap bequeathed it with high visible light activity and the ability to efficiently separate electrons and hole leading to its pollutant degradation tendency [26].
Bismuth oxyiodide (BiOI) has a stacked tetragonal structure that contains alternate [Bi2O2]2+ and I slabs. It is one of the attractive nanoparticles for visible light photocatalytic applications owing to its relatively narrow band gap (1.6 to 1.9 eV) which endowed it with high visible light activity. Photo-generated electrons and holes are also perfectly separated in BiOI as a result of the presence of strong intralayer and weak van der Waals interlayer bonding in its structure [28]. As a result, BiOI has been successfully applied in some photocatalytic processes including organic pollutant degradation, CO2 conversion and hydrogen generation.
BiPO4 is an intrinsic p-type semiconductor with two polymorphic phases. These phases include the stable monazite-type structure (known as low-temperature monoclinic phase (LBP)) and high-temperature monoclinic phase (HBP). The HBP polymorph is obtained by heating LBP at higher temperatures. BiPO4 nanoparticles are known to be non-toxic and have low costs of production [29]. They possess high thermal and chemical stability, redox active species, and high photocatalytic activity [29]. Consequently, these materials have been used for Li-ion batteries, sensors and as photocatalysts for disinfection of water and photodegradation of organic pollutants in water [30].
Bi3NbO7 is noted for its favourable properties resulting in its use as electrochemical controllers, a catalyst for photolytic water splitting, selective oxidation of hydrocarbons and as oxygen sensors [31]. It exists in cubic and tetragonal phases and has the ability to undergo a reversible transition between tetragonal phase at 800°C to the cubic phases at 900°C and back to tetragonal phase. The cubic phase has defective fluorite-structure (Fm3m, a = 0.548), while the bismuth and niobium atoms are dispersed over similar crystallographic locations. [31].
Bismuth-based nanoparticles are receiving substantial consideration as promising photocatalysts as a result of their comparatively narrow band gaps. They are non-toxic and have the potential to resist corrosion. They are environmentally friendly and relatively cheap [32]. There are a number of available reports regarding the efficient visible light activities of these nanoparticles, and their use for water disinfection and organic pollutants degradation [33]. Their effectiveness as photocatalysts for production of hydrogen gas from water as well as carbon dioxide conversion to useful hydrocarbon products has also been studied. Notwithstanding all these advantages, bismuth-based nanoparticles have some disadvantages that limit their practical application as effective photocatalysts. For example, they have small specific surface areas which impair their photocatalytic activities. They also experience recombination of the photo-generated electrons and holes [34] and thus reduce their effectiveness as photocatalysts.
Attempts to overcome these problems and improve the efficiency of these nanoparticles have culminated in the use of different approaches/techniques to modify them. These approaches comprise the use of carbon-based materials and modification with biopolymers [35], doping with metals and non-metal [36], and the use of heterostructures/mixed metal oxides [37]. The modified bismuth-based nanoparticles are reported to display higher photocatalytic activities compared to their bare/pure counterparts. Some of the photocatalytic processes to which these materials have been applied are discussed in the subsequent sections.
A number of publications are available on the use of modified bismuth-based nanoparticle for water treatment through the degradation of organic pollutants and removal of bacteria. This section presents some of the research works that have been performed in this regard.
Harmful organic contaminants in water can be degraded or mineralised into innocuous/inoffensive products (CO2 and H2O) through a photocatalytic reaction involving photo-generated electrons and holes and reactive oxygen species. Photodegradation of organic contaminants through the use of bismuth-based nanoparticles occurs when the photocatalyst absorbs light of appropriate wavelength from sunlight or illuminated light source. This light energy excites and promotes electrons in the photocatalyst’s valence band to its conduction band. This results in the creation of positive charges (holes) and negative charges (electrons) on the valence and conduction bands respectively leading to the creation of electron-hole pairs. The hole oxidise water molecule into hydrogen gas and hydroxyl radical while the electron reduces oxygen molecules into superoxide radicals. The hydroxyl and the superoxide radicals then attack the pollutants and degrade them into harmless products [38]. These hydroxyl ions and superoxide radicals are also responsible for inactivation of bacteria through degradation of their cell walls [38]. The mechanism of the photodegradation process is presented in Figure 3.
Mechanism of photocatalytic degradation of organic polluting.
A modified bismuth-based nanocomposite consisting of α-BiO3, silver (Ag) and graphene oxide (GO) (Ag/GO/α-Bi2O3), has been synthesised by [39] and deployed in photodegradation of crystal violet and rhodamine 6G dyes by visible light illumination. The Ag/GO/α-Bi2O3 exhibited six times photocatalytic activity compared to Degussa-P25. It degraded both dyes at a higher efficiency than the bare α-BiO3 and achieved about 90% degradation of the crystal violet and rhodamine 6G dyes in 40 minutes and 150 minutes respectively. Nickel doped Bi2S3 has also been applied in the degradation of congo red and rose bengal dyes by visible light illumination with successful results [40]. A nanocomposite consisting of BiVO4, Ag and reduced graphene oxide (rGO) was also synthesised and used to degrade rhodamine B dye [41]. They identified the composite to possess more photocatalytic reaction sites because of enhanced charge carriers separation ability of the BiVO4, electron transfer property of the silver nanoparticles and surface plasmon effect. The composite showed enhanced visible light activity and exhibited higher degradation efficiency of the dye compared to the bare BiVO4 and the BiVO4-rGO composite.
Qu and Huanyan [42] synthesised a BiOClxBr1-x photocatalysts consisting of BiOCl, BiOBr, BiOCl0.5Br0.5, BiOCl0.75Br0.25 and BiOCl0.25Br0.75. The photocatalytic degradation abilities of the catalysts were assessed by applying them to degrade methyl orange under ultraviolet light. BiOCl0.5Br0.5 was identified to be the best photocatalyst for the degradation of 5 mg/L of the dye at pH 7 with 90% degradation efficiency within 90 min. In addition, BiOI-graphene nanocomposite’s photodegradation ability was tested on methyl orange. The BiOI-graphene was found to degrade the dye at a faster rate than BiOI. The enhanced photodegradation efficiency of the BiOI-graphene composite was credited to its ability to effectively separate and transport the generated electrons and holes owing to the bonding between graphene and BiOI, the increase light adsorption and the high dye adsorption [43]. Studies on the photocatalytic degradation ability of Bi2WO6-rGO nanocomposite was performed by Rajagopal et al. [44] with impressive results. The improved performance of the catalyst against the degradation of rhodamine B was assigned to the fact that the catalyst possessed a large surface area, as well as the capability to reduce the rate at which the electrons and holes recombined as a result of the inclusion of rGO. Similarly, Bi2O2CO3/ZnWO4 nanocomposite was synthesised and used to degrade methylene blue [45]. Compared to the individual ZnWO4 and Bi2O2CO3, the Bi2O2CO3/ZnWO4 demonstrated excellent ability to photocatalytically degrades the dye [45]. This was as a result of the existence of a heterojunction in the composite. The presence of the heterojunction favoured the separation of the holes and electrons [45].
The occurrence and accumulation of pharmaceutical products in water bodies can be injurious to humans as well as aquatic organisms. Hence the need for an appropriate technology for the removal of this pollutants becomes paramount. Scientists have been studying photocatalysis as a suitable means to remove these pollutants. As a result, a number of photocatalytic degradation studies using bismuth-based nanoparticles have been carried out. Some of these research works have been discussed here.
In their study, [46] synthesised a Bi2WO6/Fe3O4 heterojunction through the hydrothermal process and supported it over graphene sand composite by in situ wet impregnation method. The tendency of the composite (Bi2WO6/Fe3O4/GSC) to photocatalytically degrade pharmaceutical waste was tested by its application in the degradation of oxytetracycline and ampicillin. They obtained a high degradation efficiency of the antibiotics into CO2, H2O and NO3− under solar light irradiation due to high adsorption property of the composite. The magnetic nature of the catalyst ensured its easy separation and recyclability [46]. Tetracycline degradation with BiFeO3 prepared through hydrothermal method was also undertaken with successful results [47]. BiOBr modified with chelating agents (citric acid and ethylenediaminetetraacetic acid) was reported to have been used in the degradation of norfloxacin with high photocatalytic efficiency [48]. The chelating agents modified BiOBr was noted to be more photoactive and displayed higher degradation efficiency compared to the bare BiOBr. Again, a successfully prepared BiOBr-activated peroxymonosulfate system (BiOBr/PMS) demonstrated exceptional visible-light-responsive activities for photodegradation of Ciprofloxacin [49] and carbamazepine [50] respectively. A mesoporous Bi2WO6 prepared by hydrothermal technique was used to degrade tetracycline in water, further endorsing the visible-light-driven photodegradation of pharmaceutical wastes using bismuth-based nanoparticles [51]. About 97% of the pollutant (20 mg/L) was degraded after 120 minutes of simulated solar light irradiation.
The need for cost-effective and non-toxic antibacterial agents for an effective water treatment has become urgent due to the life-threatening consequences of water pollution with various species of bacteria. The use of nanoparticles as disinfection systems for water treatment is gaining recognition due to its effectiveness. Bismuth-based nanoparticles are among the category of nanoparticles that are being tested for water disinfection. Some of the progress that has been made so far with respect to the use of bismuth-based nanoparticle for bacterial inactivation in water is discussed below:
Inactivation of Escherichia coli was determined through the use of Z-scheme photocatalyst of AgI/BiVO4 synthesised through chemical deposition precipitation [52]. The catalyst could inactivate 7.0 × 107 CFU/mL of the bacteria species within 50 minutes under visible light. Superoxide radical (•O2) and holes (h+) were identified to be responsible for the photocatalytic disinfection process. In much the same manner, Escherichia coli inactivation under visible light was performed by using Ag/BiVO4 nanocomposite with impressive results [53]. There was a total inactivation of the bacterial cell (107 CFU mL−1) within 120 minutes. They assigned the effectiveness of the composite for the bacterial inactivation to the presence of the metallic silver nanoparticle in the composite. The silver nanoparticle trapped the generated electrons and hence promoted charge carriers separation for the creation of the necessary reactive oxygen species. Zhang et al. [54] reported the application of AgBr−Ag − Bi2WO6 nanocomposite in photodisinfection of Escherichia coli K-12 by visible light illumination. The AgBr−Ag − Bi2WO6 was more effective than the other catalysts i.e. Bi2WO6 superstructure, Ag-Bi2WO6 and AgBr-Ag-TiO2 used in this experiment. The AgBr−Ag − Bi2WO6 nanocomposite was able to completely disinfect 5 x 107 cfu mL−1 of the Escherichia coli K-12 under 15 minutes through the influence of hydroxyl radicals (•OH).
A Bi2O3 and NiFe2O4/Bi2O3 photocatalysts with different concentration of NiFe2O4 were fabricated and applied in a comparative photocatalytic degradation of tetracycline in water [55]. The NiFe2O4/Bi2O3 was more efficient that Bi2O3 in the visible light degradation process with NiFe2O4/Bi2O3 (50%NiFe2O4) being the most efficient catalyst. This catalyst demonstrated a high degradation efficiency of 90.78 within 90 minutes. The catalyst was easily recovered and recycled due to its magnetic nature [55]. The destruction of bacteria cells (Escherichia coli K-12) using Bi2MoO6 –rGO was also noted to achieve high efficiency [56]. In all these cases, large surface area for enhanced pollutant adsorption, improved electron-hole reparation and the subsequent generation of sufficient oxygen reactive species were identified to be responsible for the impressive photocatalytic performance of the composites.
The release of carbon dioxide (CO2) into the atmosphere resulting mainly from fossil fuels combustion is contributing significantly to the global climate change. This phenomenon necessitates the need for appropriate strategies to abate the increasing level of CO2 in the atmosphere. An appropriate approach to reducing the level of atmospheric CO2 is its conversion into useful chemicals. Photocatalytic reduction of CO2 to useful chemicals as a way of recycling it to a fuel feedstock is receiving attention as an appropriate substitute for fossil fuels combustion [57].
The mechanism of CO2 photoreduction to hydrocarbon fuels is similar to that of organic pollutants degradation. This process also involves illumination of the semiconductor photocatalyst with a photon of appropriate energy resulting in the creation of electron and hole pairs on the conduction and valence bands respectively. The generated electrons must have greater energy than the reduction potential of CO2 i.e. the conduction band potential of the catalyst should have higher negative value than the reduction potential of CO2. At the same time, the valence band potential of the catalyst must have higher positive value than water oxidation potential. In other words, the hole must have the potential to oxidise water to produce hydrogen ion (H+) [58]. The notable thing about this process is that the type of hydrocarbon produced depends on the number of protons present in the reaction system. The possible reactions involved in the reduction/conversion of CO2 to various hydrocarbon products are presented in Eqs. 1 to 4 [59]:
The presence of two protons (H+) in the system leads to the conversion of CO2 to Carbon monoxide (CO) i.e.:
Methanol (CH3OH) is produced when six protons are available in the reaction system:
The availability of eight and twelfth protons results in the production of methane and ethanol respectively:
In this section, we discuss some of the achievement made so far as the use of bismuth-based nanocomposites in CO2 photoconversion to useful hydrocarbon products is concerned.
A comparative study on CO2 photocatalytic conversion using titanium oxide (TiO2) nanotubes and palladium decorated bismuth titanate was conducted by Raja et al. [60]. The experiment was executed through light illumination of the catalyst in a CO2 saturated sulphuric acid solution. Formic acid (HCOOH) was the resultant product. According to their result, the palladium decorated bismuth titanate nanocomposite was the better of the two catalysts as it produced about two times formic acid than that produced by the TiO2 nanotubes composite. They attributed the effectiveness of the palladium decorated bismuth titanate to effective charge carriers’ separation. In addition, a Bi4O5BrxI2-x, Bi4O5Br2 and Bi4O5I2 composite solutions which were prepared by the molecular precursor method were applied in CO2 photocatalytic reduction experiment [61]. The results showed that the Bi4O5BrxI2-x composite exhibited the highest photocatalytic activity with the Bi4O5BrI (x = 1) being the best catalyst. This catalyst (Bi4O5BrI) was able to convert CO2 to carbon monoxide (CO) at the rate of 22.85 μmol h−1g−1CO generation. High CO2 adsorption tendency and excellent electron-hole separation were identified to be the reason for the effectiveness of this catalyst for the reduction of CO2 to CO.
Again, different structures of Bi2S3 (nanoparticles and microsphere hierarchical nanostructure) prepared by Chen et al. [62] through facile and template-free solvothermal route were used to convert CO2. The microsphere composite exhibits a better visible light photocatalytic CO2 conversion activity than the Bi2S3 nanoparticle. The CO2 was reduced to formate in methanol. Excellent light harvesting ability, profound permeability and the unique hierarchical structure are the factors that accounted for the effectiveness of the Bi2S3 microsphere hierarchical nanostructure. Palanichamy et al. [63] also showed the trend in the photocatalytic performance of BiVO4, and Cu2BiVO4 in the CO2 conversion to methanol. The percentage CO2 conversion efficiencies of the BiVO4 and Cu2BiVO4 were 2.78% and 2.50% respectively within 80 minutes under the same conditions.
The ever-increasing air pollution as a result of fossil fuels combustion has heightened the need to develop alternative fuel sources. One of the alternative sources is hydrogen gas production through photocatalytic splitting of water [64]. In order to achieve an economically feasible hydrogen generation through photocatalysis, the photocatalyst must be visible light active so as to effectively utilise the limitless and readily available visible light [64]. Bismuth-based nanocomposites are highly active under visible light owing to their narrow band gaps. Consequently, generation of hydrogen gas using bismuth-based nanoparticles/composites with visible light is regarded as one of the promising approaches. The mechanism of this process is discussed as follows [59]:
Similar to the mechanism of photodegradation of organic compounds, electron and hole are produced on the conduction and valence bands of the photocatalyst when it is exposed to light with energy greater than or equal its band gap. Modification of the catalyst enhances its ability to minimise the recombination of the holes and the electrons upon generation. The holes in the valence band directly oxidise the chemisorbed water molecule on the catalyst’s surface resulting in the generation of four hydrogen ions (H+) and oxygen molecules (O2):
The conduction band electrons then reduce the hydrogen ions to produce hydrogen gas:
A number of experimental results on the utilisation of visible light active bismuth-based nanocomposite for production of hydrogen through water splitting have been published. Some of these published results are discussed in this section.
The ability of a bismuth-based catalyst, Cr2O3/Pt/RuO2:Bi2O3, to photocatalytically split water into hydrogen gas was studied in the presence of a sacrificial hole scavenger (oxalic acid) by Hsieh et al. [65]. According to their result, the photocatalyst showed a high ability to generate hydrogen gas from water at a rate of 17.2 μmol g−1 h−1. In their experiment, Adhikari et al. [66] carried out the synthesis and characterisation of visible light active bismuth-based photocatalysts (Ta2O5/Bi2O3, TaON/Bi2O3, and Ta3N5/Bi2O3). They then evaluate their tendency to generate hydrogen from water under visible light using water-methanol solution. The result showed enhanced hydrogen generation potential of the catalysts. The composites showed significant hydrogen production in comparison to the individual component (Ta2O5, Bi2O3, TaON and Ta3N5) as a result of the existence of heterojunction in the composites. The heterojunction enhanced separation of the electrons and holes. In addition, the synthesis, characterisation and the photocatalytic hydrogen gas production tendency of Pt-Bi2O3/RuO2 under visible light was also assessed [67]. The experiment was performed by adding 0.3 M Na2SO3 and 0.03 M H2C2O4 as sacrificial agents. The presence of Na2SO3 and H2C2O4 assisted the catalyst to increase hydrogen production at the rates of 11.6 mol g−1 h−1 (Na2SO3) and 14. 5 mol g−1 h−1 (H2C2O4) [67].
The desire to purify urban or indoor air by removing nitrogen oxide pollutants (NOX) and volatile organic compounds (VOCs) from it particularly in public places including schools, churches, shopping mall and so on, has become an issue of high necessity. This is due to the health consequences associated with these groups of pollutants which are mostly released into the air through vehicular emissions, building materials, personal care products, office equipment, cleaning agents etc. [68]. Photocatalysis has been identified as an appropriate technology for the removal of these pollutants from the air because of the technique’s tendency to completely mineralise these pollutants [68].
The principle behind the photocatalytic degradation of the NOX and VOCs in the air is similar to that described in the previous sections: The holes generated after excitation of electrons from the valence band to the conduction band due to illumination of the catalyst oxidise water molecules in the air to for •OH. The •OH then attach the organic pollutants in air and mineralise them through the destruction of their molecular bonds.
Bismuth-based photocatalysts are among the catalysts that have been tested for effective air purification experiments. Some results of these experiments are discussed here:
The successful application of Bi nanoparticles modified TiO2 (Degussa P25) with mixed anatase and rutile phase in the photocatalytic removal of NO from the air at ppb level was undertaken by Zhao et al. [69]. The Bi-TiO2 was noted to outperform the pure TiO2 in the NO photocatalytic removal process. Among the catalysts used, Bi-TiO2 with Bi nanoparticles diameters ranging from 5 to 8 demonstrated excellent photocatalytic activity as this diameter range acted as an excellent visible light active site with improved charge separation [69]. The improved performance of this catalyst was assigned to the movement of the electrons, which were generated through plasmonic activation of the Bi nanoparticles, between the conduction band of the anatase and rutile phases of TiO2; thus reducing their rate of recombination with the holes. In their experiment, Ai et al. [70] compared the ability of a hierarchial BiOBr microsphere, BiOBr bulk, Degussa TiO2 and C doped TiO2 to photocatalytically remove NO from indoor air (400 ppb level). According to their result, the BiOBr microsphere performed extremely well compared to the other catalysts as a result of its unique hierarchical structure which enhanced the diffusion of intermediates and NO oxidation final product leading to the efficient removal of the NO. NO removal from air at ppb levels through visible light photocatalysis has also been studied by [71, 72] using N-Bi2O2CO3-graphene quantum dot and Br-BiOCOOH respectively with excellent results.
Photocatalytic decomposition experiment was also performed to remove toluene from air. The experiment was conducted comparatively using V2O5/BiVO4/TiO2, V2O5/BiVO4 and TiO2 photocatalysts through illumination with visible light. The V2O5/BiVO4/TiO2 was identified to be the best catalyst for the decomposition of toluene due to enhanced charge carriers separation across the multiple interfaces of the ternary nanojunctions [73]. Similarly, toluene removal from air through photocatalysis using BiOI/TiO2, pure TiO2 and Degussa P25 was carried out by Boonprakob et al. [74]. They observed that the highest toluene photodecomposition activity (ca. 68%) was exhibited by BiOI/TiO2 as a result of its excellent visible light activity and efficient charge carriers separation. In their study, Xu et al. [75] synthesised Bi2O3/TiO2 nanocomposite and tested its ability to photocatalytically decompose 4-chlorophenol in air. They noted that the Bi2O3/TiO2 catalyst effectively removed the pollutant from air compared to the pure TiO2 and Degussa P25 owing to the narrow band gap of α- Bi2O3 which improved on the visible light activity of the composite.
The necessity to develop more efficient photocatalysts for effective water treatment, carbon dioxide conversion, hydrogen reduction and air purification so as to alleviate the increasing energy crisis, air pollution, and to make clean and potable water readily available cannot be overemphasised. The use of bismuth-based nanoparticles/nanocomposite in this regard has been organised in this chapter. The chapter also provided recently generated information on the use of bismuth-based nanoparticles in various photocatalytic degradation processes. A detailed discussion was provided on bismuth as an element/metal, and bismuth-based nanoparticles including bismuth chalcogenides, bismuth vanadate, bismuth oxyhalides and other bismuth-related nanoparticles. Attention was also paid to the modification of these nanoparticles to improve their photocatalytic activities. The application of the modified nanoparticles in various photocatalytic processes with emphasis on water treatment, waste gas treatment, hydrogen production and air purification has also been thoroughly discussed.
The incidence of microbial attack in different sectors such as food, textiles, medicine, water disinfection, and food packaging leads to a constant trend in the search for new antimicrobial substances. The increased resistance of some bacteria to some antibiotics and the toxicity to the human body of some organic antimicrobial substances has increased the interest in the development of inorganic antimicrobial substances. Among these compounds, metal and metal oxide compounds have attracted significant attention due to their broad-spectrum antibacterial activities. On the other hand, nanoscale materials are well known thanks to their increased properties due to their high surface area-to-volume ratio. Antimicrobial NPs have shown excellent and different activities from their bulk properties [1, 2].
\nDuring last decades, metal oxide nanoparticles, such as zinc oxide (ZnO), manganese oxide (MgO), titanium dioxide (TiO2), and iron oxide (Fe2O3), have been extensively applicable thanks to their unique physiochemical properties in biological applications. Among metal oxide antimicrobial agents, TiO2 is a valuable semiconducting transition metal oxide material and shows special features, such as easy control, reduced cost, non-toxicity, and good resistance to chemical erosion, that allow its application in optics, solar cells, chemical sensors, electronics, antibacterial and antifungal agents [3]. In general, TiO2 nanoparticles (TiO2 NPs) present large surface area, excellent surface morphology, and non-toxicity in nature. Several authors have reported that TiO2 NPs have been one of the most studied NPs thanks to their photocatalytic antimicrobial activity, exerting excellent bio-related activity against bacterial contamination [4, 5, 6, 7].
\nAntimicrobial activity of nanoparticles is highly influenced by several intrinsic factors such as their morphology, size, chemistry, source, and nanostructure [8, 9, 10, 11]. Specifically, antimicrobial activity of TiO2 NPs is greatly dependent on photocatalytic performance of TiO2, which depends strongly on its morphological, structural, and textural properties [12]. Several TiO2 NPs have been developed through different methods of synthesis. Specifically, in this chapter, eco-friendly synthesis based on biological sources, such as natural plant extracts and metabolites from microorganisms, which have resulted in TiO2 NPs with different size, shape, morphology, and crystalline structures will be presented. Titanium dioxide produces amorphous and crystalline forms and primarily can occur in three crystalline polymorphous: anatase, rutile, and brookite. Studies on synthesis have stated that the crystalline structure and morphology of TiO2 NPs is influenced by process parameters such as hydrothermal temperatures, starting concentration of acids, etc. [13]. The crystal structures and the shape of TiO2 NPs are both the most important properties that affect their physicochemical properties, and therefore their antimicrobial properties [14]. Regarding the crystal structures, anatase presents the highest photocatalytic and antimicrobial activity. Some works have shown that anatase structure can produce OH˙ radicals in a photocatalytic reaction, and as it will be clearly explained below, bacteria wall and membranes can be deadly affected [15, 16].
\nThe potential health impact and toxicity to the environment of NPs is currently an important matter to be addressed. Several works have confirmed that metal oxide NPs conventionally synthesized using chemical methods, such as sol–gel synthesis and chemical vapor deposition, have shown different levels of toxicity to test organisms [17, 18, 19, 20]. In recent years, researchers have emphasized on the development of nanoparticles promoted through environmental sustainability and processes characterized by an ecological view, mild reaction conditions, and non-toxic precursors. Due to this growing sensitivity toward green chemistry and biological processes, ecological processes are currently being investigated for the synthesis of non-toxic nanoparticles.
\nThese biological methods are considered safe, cost-effective, biocompatible, non-toxic, sustainable, and environmentally friendly processes [20]. Furthermore, it has been described that chemically synthesized NPs have exhibited less stability and added agglomeration, resulting in biologically synthesized NPs that are more dispersible, stable in size, and the processes consuming less energy [21].
\nThese biosynthetic methods, also called “green synthesis,” use various biological resources available in nature, including live plant [22], plant products, plant extracts, algae, fungi, yeasts [23], bacteria [24], and virus for the synthesis of NPs. Among these methods, the processes that use plant-based materials are considered the most suitable for large-scale green synthesis of NPs with respect to their ease and safety [25]. On the other hand, the reduction rate of metal ions in the presence of the plant extract is much faster compared to microorganisms, and provides stable particles [26]. Plants contain biomolecules that have been highly studied by researchers like phenols, nitrogen compounds, terpenoids, and other metabolites. It is well known that the hydroxyl and carboxylic groups present in these biocompounds act as stabilizers and reducing agents due to their high antioxidant activity [12]. Thus, plant extracts have been studied as one of the best green alternatives for metal oxide nanoparticles synthesis [27]. In recent years, TiO2 nanoparticles have been obtained by using different plant extracts, but not all of them have been studied for their antimicrobial activity. Table 1 presents a compilation of synthesized TiO2 nanoparticles from green synthesis by using plant extracts that were tested against different microorganisms.
\nSource | \nTitanium precursor | \nSize (nm) | \nShape/crystal structure | \nTarget microorganism (method) | \n
---|---|---|---|---|
\nAzadirachta indica leaves extract [28] | \nTiO2\n | \n25–87 (SEM) | \nSpherical/anatase-rutile | \n\nS. typhi, E. coli, and K. pneumoniae (broth micro dilution method) | \n
\nPsidium guajava leaves extract [29] | \nTiO(OH)2\n | \n32.58 (FESEM) | \nSpherical shape and clusters/anatase-rutile | \n\nS. aureus and E. coli (agar diffusion) | \n
\nVitex negundo Linn leaves extract [30] | \nTi{OCH(CH3)2}4\n | \n26–15 (TEM) | \nSpherical and rod shaped/tetragonal phase anatase | \n\nS. aureus and E. coli (agar diffusion) | \n
\nMorinda citrifolia leaves extract [31] | \nTiCl4\n | \n15–19 (SEM) | \nQuasi-spherical shape/rutile | \n\nS. aureus, B. subtilis, E. coli, P. aeruginosa, C. albicans, A. niger (agar diffusion) | \n
\nTrigonella foenum-graecum leaf extract [21] | \nTiOSO4\n | \n20–90 (HR-SEM) | \nSpherical/anatase | \n\nE. faecalis, S. aureus, S. faecalis, B. subtilis., Y. enterocolitica, P. vulgaris, E. coli, P. aeruginosa, K. pneumoniae, and C. albicans (agar diffusion) | \n
Orange peel extract [32] | \nTiCl4\n | \n20–50 (SEM) | \nIrregular and angular structure with high porous net/anatase | \n\nS. aureus, E. coli, and P. aeruginosa (agar diffusion) | \n
\nGlycyrrhiza glabra root extracts [33] | \nTiO2\n | \n60–140 (FESEM) | \nSpherical shape/anatase | \n\nS. aureus and K. pneumoniae (agar diffusion) | \n
Synthesis of TiO2 NPs by using plant extracts.
Different factors need to be evaluated in this research field in order to obtain TiO2 NPs with better properties and to maintain their biocompatibility. It has been shown that nanoparticles obtained from green synthesis can have a better morphology and size translated into better antimicrobial activity. Mobeen and Sundaram have obtained TiO2 NPs from titanium tetrachloride precursor through a chemical and a green synthesis method. Sulfuric acid and ammonium hydroxide were used in the chemical-based method and, in the green synthesis, those chemical reagents were replaced by an orange peel extract [32]. The nanoparticles obtained by using the natural extract presented a well-defined and smaller crystalline nature (approx. 17.30 nm) compared to the nanoparticles synthesized through the chemical method (21.61 nm). Both methods resulted in anatase crystalline structures, and, when evaluating the antimicrobial activity, the more eco-friendly NPs revealed higher bactericidal activity against Gram-positive and Gram-negative bacteria compared to the chemically synthesized nanoparticles.
\nBavanilatha et al. have also detailed TiO2 NPs green synthesis with Glycyrrhiza glabra root extract. Antibacterial activity against Staphylococcus aureus and Klebsiella pneumonia were investigated and in vivo toxicity tests using the zebrafish embryonic model (Danio rerio) were also carried out [33]. Results have demonstrated their biocompatibility because healthy embryos of adult fish to different variations of NP and no distinctive malformations were observed at every embryonic stage with respect to embryonic controls.
\nSubhapriya and Gomathipriya have biosynthesized TiO2 NPs by using a Trigonella foenum-graecum leaf extract, obtaining spherical NPs and their size varied between 20 and 90 nm, and their antimicrobial activity was evaluated through the standard method of disc diffusion [21]. The NPs showed significant antimicrobial activity against Yersinia enterocolitica (10.6 mm), Escherichia coli (10.8 mm), Staphylococcus aureus (11.2 mm), Enterococcus faecalis (11.4 mm), and Streptococcus faecalis (11.6 mm). Results confirmed developed TiO2 NPs as an effective antimicrobial drug that can lead to the progression of new antimicrobial drugs.
\nSpherical TiO2 NPs were synthesized from plants, in particular by applying a Morinda citrifolia leaf extract, and through advanced hydrothermal method [31]. Developed TiO2 NPs showed a size between 15 and 19 nm in an excellent quasispherical shape. In addition, their antimicrobial activity was tested against human pathogens, such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Candida albicans, and Aspergillus niger. TiO2 NPs exhibited interesting antimicrobial activity, principally against Gram-positive bacteria.
\nIn addition to plants, other organisms can produce inorganic compounds at an intra or extracellular level. The synthesis of TiO2 NPs through microorganisms, including bacteria, fungi, and yeasts, also meets the requirements and the exponentially growing technological demand toward eco-friendly strategies, by avoiding the use of toxic chemicals in the synthesis and protocols [34]. The metabolites generated by microorganism present bioreducing, capping, and stabilizing properties that improve the NPs synthesis performance. Jayaseelan et al. have stated glycyl-L-proline, one of the most abundant metabolite from Aeromonas hydrophilia bacteria, as the main compound that acted as a capping and stabilizing agent during TiO2 NPs green synthesis [35]. Moreover, the interest in fungi in green synthesis of metal oxide nanoparticles has increased over last years. Fungi enzymes and/or metabolites also present intrinsically the potential to obtain elemental or ionic state metals from their corresponding salts [34, 36]. Different works based on the green synthesis of TiO2 NPs from bacteria and fungus are presented in Table 2. Some of them have been synthesized with antimicrobial and antifungal purposes, and their target microorganisms are also declared.
\nMicroorganism | \nTitanium precursor | \nSize (nm) | \nShape/crystal structure | \nTarget microorganisms (method) | \n
---|---|---|---|---|
\nAeromonas hydrophilia [46] | \nTiO(OH)2\n | \n28–54 (SEM) ~ 40.5 (XRD) | \nSpherical/uneven | \n\nS. aureus, S. pyogenes (agar diffusion) | \n
\nAspergillus flavus [34] | \nTiO2\n | \n62–74 (TEM) | \nSpherical/anatase and rutile | \n\nE. coli, P. aeruginosa, K. pneumoniae, B. subtilis (agar diffusion and MIC) | \n
\nBacillus mycoides [37] | \nTitanyl hydroxide | \n40–60 (TEM) | \nSpherical/anatase | \n\nE. coli (toxicity) | \n
\nBacillus subtilis [38] | \nK2TiF6\n | \n11–32 (TEM) | \nSpherical | \nAquatic biofilm | \n
\nFusarium oxysporum [36] | \nK2TiF6\n | \n6–13 (TEM) | \nSpherical/brookite | \n— | \n
\nLactobacillus sp. [51] | \nTiO(OH)2\n | \n~ 24.6 (TEM) | \nSpherical/anatase-rutile | \n— | \n
\nPlanomicrobium sp. [39] | \nTiO2\n | \n100–500 (SEM) | \nIrregular/pure crystalline | \n\nB. subtilis, K. planticola, Aspergillus niger (agar diffusion) | \n
\nPropionibacterium jensenii [52] | \nTiO(OH)2, 300°C | \n15–80 (FESEM) | \nSpherical | \n— | \n
\nSaccharomyces cerevisiae [51] | \nTiO(OH)2\n | \n~ 12.6 (TEM) | \nSpherical/anatase-rutile | \n\n—\n | \n
Examples of TiO2 NPs synthesis through microorganisms, both bacteria and fungus strains.
Two important factors that affect NPs synthesis are the type of microorganisms and their source. Some microorganisms widely used in the food industry are Lactobacillus, a bacterium used in dairy products and as a probiotic supplement, and Saccharomyces cerevisiae, a yeast commonly used in bakery. Jha et al. have investigated the effectiveness of both microorganisms to synthesize TiO2 NPs. A comparison between synthesis through Lactobacillus from yogurt and probiotic tablets resulted in different NP sizes: a particle size of 15–70 nm for yogurt, and 10–25 nm for tablets. This difference was due to the purity of the bacteria [40]. In general, TiO2 NP synthesis through microorganisms has not provided stable sizes, being not industrially scalable compared to the synthesis of nanoparticles from plants.
\nHarmful bacteria, such as Staphylococcus aureus, Burkholderia cepacia, Pseudomonas aeruginosa, Clostridium difficile, Klebsiella pneumoniae, Escherichia coli, Acinetobacter baumannii, Mycobacterium tuberculosis, and Neisseria gonorrhoeae, are responsible for bacterial infections that can cause serious diseases in humans year after year [40]. The principal solution is the use of antibiotics, antimicrobial and antifungal agents. Nevertheless, in recent years there has been an increase in the resistance of several bacterial strains to these substances, and therefore there is currently a great interest in the search for new antimicrobial substances. The antimicrobial nanoparticles have been studied due to their high activity, specifically the metal oxide nanoparticles [41, 42, 43]. In this sense, titanium dioxide nanoparticles are one of the antimicrobial NPs whose study has gained interest during last years.
\nTiO2 is a thermally stable and biocompatible chemical compound with high photocatalytic activity and has presented good results against bacterial contamination [44]. Table 3 presents some research including the antimicrobial capacity of TiO2 NPs.
\nMicroorganism | \nNPs | \nResults | \n
---|---|---|
Methicillin-resistant Staphylococcus aureus [45] | \nFe3O4-TiO2 core/shell magnetic NPs | \nThe survival ratio [%] of bacteria decreased from 82.40 to 7.13%. | \n
\nStaphylococcus saprophyticus [45] | \nFe3O4-TiO2 core/shell magnetic NPs | \nThe survival ratio [%] of bacteria decreased from 79.15 to 0.51%. | \n
\nStreptococcus pyogenes[57] | \nFe3O4-TiO2 core/shell magnetic NPs | \nThe survival ratio [%] of bacteria decreased from 82.87 to 4.45%. | \n
\nEscherichia coli [46] | \nTiO2 nanotubes ~ 20 nm | \n97.53% of reduction | \n
\nStaphylococcus aureus [46] | \nTiO2 nanotubes ~ 20 nm | \n99.94% of reduction | \n
\nBacillus subtilis [47] | \nTiO2 NPs co-doped with silver (19–39 nm) | \n1% Ag-N-TiO2 had the highest antibacterial activity with antibacterial diameter reduction of 22.8 mm | \n
\nMycobacterium smegmatis [48] | \nCu-doped TiO2NPs ~20 nm | \nThe percentage of inhibition was around 47% | \n
\nPseudomonas aeruginosa [49] | \nTiO2 NPs 10–25 nm | \nAlthough it was not completely euthanized, their survival was significantly inhibited. | \n
\nShewanella oneidensis MR-1 [48] | \nCu-doped TiO2 NPs ~20 nm | \nThe percentage of inhibition was around 11% | \n
TiO2 nanoparticles against different microorganisms and their antimicrobial activities.
The principal factors differentiating the antimicrobial activity between TiO2 NPs were their morphology, crystal nature, and size. According to López de Dicastillo et al. [11], hollow TiO2 nanotubes presented interesting antimicrobial reduction thanks to the enhancement of specific surface area. This fact can be explained by the nature of titanium dioxide, and one of the main mechanisms of its action is through the generation of reactive oxygen species (ROS) on its surface during the process of photocatalysis when it exposed to light at an appropriate wavelength. It is important to highlight that some research works have evidenced antimicrobial activity of TiO2 NPs increased when they were irradiated with UV-A light due to the photocatalytic nature of this oxide. The time of irradiation varied between 20 min [45] and 3 hours [50].
\nTitanium dioxide nanoparticles (TiO2 NPs) are one of the most studied materials in the area of antimicrobial applications due to its particular abilities, such as bactericidal photocatalytic activity, safety, and self-cleaning properties. The mechanism referred to the antimicrobial action of TiO2 is commonly associated to reactive oxygen species (ROS) with high oxidative potentials produced under band-gap irradiation photo-induces charge in the presence of O2 [51]. ROS affect bacterial cells by different mechanisms leading to their death. Antimicrobial substances with broad spectrum activity against microorganisms (Gram-negative and Gram-positive bacteria and fungi) are of particular importance to overcome the MDR (multidrug resistance) generated by traditional antibiotic site-specific.
\nThe main photocatalytic characteristic of TiO2 is a wide band gap of 3.2 eV, which can trigger the generation of high-energy electron–hole pair under UV-A light with wavelength of 385 nm or lower [52]. As mentioned above for bulk powder, TiO2 NPs have the same mechanism based on the ROS generation with the advantage of being at nanoscale. This nanoscale nature implies an important increase of surface area-to-volume ratio that provides maximum contact with environment water and oxygen [53] and a minimal size, which can easily penetrate the cell wall and cell membrane, enabling the increase of the intracellular oxidative damage.
\nBacteria have enzymatic antioxidant defense systems like catalases and superoxide dismutase, in addition to natural antioxidants like ascorbic acid, carotene, and tocopherol, which inhibit lipid peroxidation or O-singlet and the effects of ROS radicals such as OH2˙− and OH˙. When those systems are exceeded, a set of redox reactions can lead to the death cell by the alteration of different essential structures (cell wall, cell membrane, DNA, etc.) and metabolism routes [54]. In the following sections, several ways that cellular structures were affected in the presence of TiO2 NPs will be described. In order to understand the genome responses of bacteria to TiO2-photocatalysis, some biological approaches related to expression of genes encoding to defense and repair mechanism of microorganism will explained below. Different mechanisms and processes of antimicrobial activity of TiO2 NPs are represented as a global scheme in Figure 1.
\nScheme of main antimicrobial activity-based processes.
ROS are responsible for the damage by oxidation of many organic structures of microorganisms. One of them is the cell wall, which is the first defense barrier against any injury from the environment, thus being the first affected by oxidative damage. Depending on the type of microorganism, the cell wall will have different composition; that is, in fungi and yeast, cell walls are mainly composed of chitin and polysaccharides [55], Gram-positive bacteria contain many layers of peptidoglycan and teichoic acid, and Gram-negative bacteria present a thin layer of peptidoglycan surrounded by a secondary lipid membrane reinforced with transmembrane lipopolysaccharides and lipoproteins [56]. Thus, the effect of TiO2 NPs will be slightly different depending type of microorganism.
\nIt has been studied that the composition of the cell wall in Pichia pastoris (yeast) changed in the presence of TiO2, increasing the chitin content in response to the ROS effects [57]. The cell wall of Escherichia coli (Gram-negative) composed of lipo-polysaccharide, phosphatidyl-ethanolamine, and peptidoglycan has been reported to be sensitive to the peroxidation caused by TiO2 [58]. The damage can be quantified by assessing the production of malondialdehyde (MDA), which is a biomarker of lipid peroxidation, or through ATR-FTIR of the supernatant of cell culture, which evidenced the way that porins and proteins on the outer membrane were affected, probably as a result of greater exposure to the surface of TiO2 [59]. In fungi, the release of OH˙ captured hydrogen atoms from sugar subunits of polysaccharides, which composed the cell wall, leading to the cleavage of polysaccharide chain and the exposition of cell membrane [60].
\nIn terms of genetic issues, there is evidence that the bacteria change the level expression of certain genes encoding for proteins involved in lipopolysaccharide and peptidoglycan metabolism, pilus biosynthesis, and protein insertion related to the cell wall which values were lower-expressed after exposition to TiO2 NPs [61].
\nThe second usual cellular target of most of antibiotics is the cell membrane mainly composed by phospholipids, which grant the cell a non-rigid cover, permeability, and protection. Most of the studies with TiO2 NPs have been focused to the loss of membrane integrity caused by oxidation of phospholipids due to ROS such hydroxyl radicals and hydrogen peroxide [62, 63], which led to an increase in the membrane fluidity, leakage of cellular content, and eventually cell lysis.
\nGram-positive bacteria present only one membrane protected by many layers of peptidoglycan, whereas Gram-negative bacteria are composed by two membranes, inner and outer, and a thin layer of peptidoglycan between them. The outer membrane is exposed, thus, more liable to mechanical breakage due to the lack of peptidoglycan protective cover, like in Gram-positive bacteria [64]. Some studies have demonstrated a better antimicrobial performance of TiO2 NPs against Gram-positive bacteria [65] while others reported that Gram-negative bacteria were more resistant [66, 67]. It can be concluded that the bacterial inactivation effectiveness depends mainly on the resistant capacity of cell wall structures and the damage level of ROS generation [68].
\nIn contrast with the lower expression of genes related to the cell wall seen before, the level expression of genes encoding for enzymes involved in metabolism of lipid essential for the cell membrane structure, are over-expressed [61]. It would be concluded that cells compensate the initial cell wall damage by reinforcing the second defense barrier, the cell membrane, in a way to provide support against the oxidation produced by ROS.
\nIn fungi, the biocidal effect is not quite different. In the presence of TiO2 NPs and UV light, hydroxyl radicals, hydrogen peroxide, and superoxide anions initially promote oxidation of the membrane, leading to an unbalance in the cell permeability, even decomposition of cell walls [69]. This oxidation can inhibit cell respiration by affecting intracellular membranes in mitochondria. Studies have demonstrated biocidal effects on Penicillium expansum [70], but there is still research on other strains.
\nBeyond the relatively well-studied initial lipoperoxidation attack of TiO2 NPs on the outer/inner cell membrane of the microorganism, specific mechanisms are still aimed of being solved.
\nAs the oxidative damage generates lipoperoxidation of cell membranes due to their lipid nature, the respiratory chain, which takes place in the double-membrane mitochondria, is also affected. This organelle is a natural source of ROS in aerobic metabolism because superoxide anions are produced in the electron transfer respiratory chain process. Mitochondria can control this fact by converting them into H2O2 by superoxide dismutase (SOD), and finally into water by glutathione peroxidase and catalase [71]. The presence of TiO2 NPs increases the production of ROS at levels that this enzymatic defense mechanism cannot attenuate the damage, even a dysregulation in electron transfer through the mitochondrial respiratory chain implies an increase in ROS generation [72].
\nThe genetic approaches have indicated that changes in level expression in genes related to the energy production in mitochondria prioritize the most efficient pathway to uptake oxygen, which is through ubiquinol coenzyme [61]. This coenzyme presented a higher capacity to exchange electrons, while the coenzyme-independent oxygen uptake pathways were expressed at lower level.
\nDamage at molecular level in DNA affects all regulatory microorganism metabolism, replication, transcription, and cell division. DNA is particularly sensitive to oxidative damage because oxygen radicals, specially OH˙ produced by Fenton reaction [73], may attack the sugar-phosphate or the nucleobases and cause saccharide fragmentation aimed to the strand break [74].
\nDNA strand modifications are more lethal than base modifications (punctual mutation). Mitochondrial DNA is more vulnerable to oxidative damage than nuclear DNA because it is closer to a major cellular ROS source [75].
\nBesides the enzymatic detoxification system (SOD, glutathione and catalase), DNA injuries are covered by a set of structures related to post-translational modification, protein turnover, chaperones (related to folding), DNA replication and repair, which are significantly over-expressed in the presence of TiO2 NPs [61].
\nIron is an essential ion for cell growth and survival, but it can turn potentially toxic if some malfunction in homeostatic regulation occurs (i.e., Fenton reaction that produces ROS). Bacteria are able to regulate iron concentration in order to maintain it in a physiological range [76]. This regulation involves directly siderophores to active transport of iron in cell [77], whose coding genes related to siderophore synthesis and iron transport protein are significantly lower-expressed in the presence of TiO2 NPs, decreasing the ability to assimilate and transport it, leading to cell death [61]. The loss of homeostasis regulation was confirmed by ICP-MS analysis, which revealed that the presence of TiO2 NPs significantly reduced the cellular iron level in Pseudomonas brassicacearum, directly proportional to the cell viability [78].
\nRegarding the functions related to Pi group (PO4\n3−) uptake, major differences were found in the expression of set of genes contained in Pho regulon, which were significantly lower when compared to the control [61]. The Pho regulon is a regulatory network in bacteria, yeast, plants, and animals, related to assimilation of inorganic phosphate, merely available in nature, and essential to nutritional cross-talk, secondary metabolite production, and pathogenesis [79].
\nThis suggested that the microorganisms were highly deficient in phosphorus uptake and metabolism in the presence of TiO2 NPs. It should be also noted that the Pho regulon has been reported to regulate biofilm synthesis capacity and pathogenicity [80].
\nTiO2 NPs can directly oxidize components of cell signaling pathways and even change the gene expression by interfering with transcription factors [81]. There is evidence to confirm the interference of TiO2 NPs in biosynthesis pathways of signaling molecules that bind lipopolysaccharide, stabilize and protect the cell wall against oxidative damage [82]. Moreover, a significant decrease in the synthesis of quorum-sensing signal molecule related to functions like pathogenesis and biofilm development was observed. This was corroborated through Scanning Electron Microscopy (SEM) images of bacteria (P. aeruginosa) growth in the presence of TiO2 NPs without UV irradiation. Cells appeared mainly non-aggregated and dispersed in the substratum, compared with controls without NPs where cells were mainly aggregated by lateral contact. This suggested that TiO2 NPs not only affected microorganisms by oxidative damage, but also bacteria aggregation and biofilm formation, which directly influenced in pathogenicity [83].
\nIn plants and algae, ROS can act as signaling intermediates in the process of transcription factor controlling stress response by H2O2, which is activated by a GSH peroxidase, and not by peroxides directly. But there is still lack of research in this area [84].
\nThe control of morphology and crystal structure of TiO2 NPs is the most important factor to enhance their antimicrobial activity. The appropriate design based on desirable surface properties given by shaped nanoparticles can improve effectiveness that is also dependent on the type of bacteria. The route of synthesis of TiO2 NPs is also a key factor. Recent works have revealed more eco-friendly synthesis methods, principally based on plant-based compounds and microorganisms, such as bacteria and fungus. Antimicrobial activity of different TiO2 NPs against Gram-positive and Gram-negative bacteria including antibiotic-resistant strains has been confirmed in different works.
\nSpecific studies on antimicrobial mechanisms have evidenced that microorganism exposed to photocatalytic TiO2 NPs exhibited cell inactivation at regulatory network and signaling levels, an important decrease in the activity of respiratory chain, and inhibition in the ability to assimilate and transport iron and phosphorous. These processes with the extensive cell wall and membrane alterations were the main factors that explain the biocidal activity of TiO2 NPs.
\nThe authors acknowledge the financial support of CONICYT through the Project Fondecyt Regular 1170624 and “Programa de Financiamiento Basal para Centros Científicos y Tecnológicos de Excelencia” Project FB0807, and CORFO Project 17CONTEC-8367.
\nThe authors declare no conflict of interest.
IntechOpen publishes different types of publications
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