Metal Oxide-Based Photocatalysis: Fundamentals and Prospects for Application

Metal Oxide-Based Photocatalysis

Fundamentals and Prospects for Application

First Edition

Adriana Zaleska-Medynska

Series Editor

Ghenadii Korotcenkov

Table of Contents

Cover image

Title page

Copyright

List of contributors

Series editor biography

Preface to the series

1: Introduction

1.1 Introduction

2: Fundamentals of metal oxide-based photocatalysis

Abstract

2.1 Principles of metal oxide-based photocatalysis

2.2 Requirements of metal oxides

2.3 Role of noble metals in photocatalysis

3: Metal oxide photocatalysts

Abstract

3.1 Synthesis of metal oxides used in photocatalysis

3.2 Unitary metal oxides (advantages, disadvantages, achievements)

3.3 Nanostructured MeIOx/MeIIOx heterojunction photocatalysts

3.4 Metal/MeOx photocatalysts

3.5 Composite-based photocatalysts

3.6 Outlook

4: Application of metal oxide-based photocatalysis

Abstract

4.1 Water treatment

4.1.1 Types of contamination

4.1.2 Photocatalyst immobilization

4.1.3 Photocatalytic reactors

4.1.4 Effect of reaction parameters on the photocatalytic process

4.1.5 Scale-up process and prospects

4.2 Hydrogen production

4.2.1 Basic principle of photocatalytic hydrogen generation by water splitting

4.2.2 Strategies for achieving photocatalytic water splitting

4.2.3 Brief overview of metal oxide semiconductors in photocatalytic water splitting

4.2.4 Chemical additives for H2 and O2 production enhancement

4.2.5 Metal oxide co-catalysts for photocatalytic water splitting

4.2.6 Evaluation of photocatalytic water splitting

4.2.7 Photoreactor design

4.2.8 Conclusions and prospects

4.3 Air depollution and volatile organic compound (VOC) removal using different photocatalysts

4.3.1 The mechanism of pollutant photo-oxidation

4.3.2 Photodisinfection of pathogens

4.3.3 Factors that impact the photocatalytic oxidation process

4.3.4 Immobilization techniques

4.3.5 Photoreactor design for photocatalytic air purification

4.3.6 Conclusions and future prospects

4.4 Hydrocarbon generation (CO2 reduction)

4.4.1 Fundamental aspects for photocatalytic reduction of CO2

4.4.2 Photocatalyst design for photocatalytic CO2 reduction

4.4.3 Important factors for photocatalytic reduction of CO2

4.4.4 Photoreactors for CO2 reduction

4.4.5 Conclusions and prospects

4.5 Photochemical transformation of specific compounds

4.5.1 Types of photocatalysts

4.5.2 Role of external conditions

4.5.3 Synthesis of organic compounds

4.5.4 Reactors for phototransformation

4.5.5 Scaling-up process and prospects

4.6 Medical applications: Application in photodynamic therapy

4.6.1 Phocatalysts

4.6.2 Light penetration

4.6.3 Conclusions and perspectives

4.7 Applications in construction, building materials, and textiles

4.7.1 Introduction

4.7.2 Superhydrophilicity mechanism

4.7.3 Exterior construction materials

4.7.4 Interior construction materials

4.7.5 New applications

4.7.6 Perspectives, problems, and limitations

4.8 Photoelectrocatalysis (PEC) for energy generation

4.8.1 Photoelectrocatalysts for solar energy conversion

4.8.2 PEC hydrogen generation

4.8.3 Conclusions and prospects

4.9 Integration and coupling of heterogeneous photocatalysis with other advanced oxidation processes

4.9.1 Photocatalytic ozonation

4.9.2 Photoelectrocatalysis

4.9.3 Heterogeneous photo-Fenton and photoelectro-Fenton methods

4.9.4 Sonophotocatalysis

4.9.5 Conclusions and prospects

5: Outlook and prospects

Index

Copyright

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List of contributors

Aleksandra Pieczyńska     University of Gdansk, Gdansk, Poland

Anna Malankowska     University of Gdansk, Gdansk, Poland

Beata Bajorowicz     University of Gdansk, Gdansk, Poland

Anna Gołąbiewska     University of Gdansk, Gdansk, Poland

Ewelina Grabowska     University of Gdansk, Gdansk, Poland

Joanna Nadolna     University of Gdansk, Gdansk, Poland

Martyna Marchelek     University of Gdansk, Gdansk, Poland

Marek P. Kobylański     University of Gdansk, Gdansk, Poland

Marta Paszkiewicz-Gawron     University of Gdansk, Gdansk, Poland

Paweł Mazierski     University of Gdansk, Gdansk, Poland

Adriana Zaleska-Medynska     University of Gdansk, Gdansk, Poland

Series editor biography

Ghenadii Korotcenkov, Research Professor (2008-present), Schoool of Materials Science and Engineering, Gwangju Institute of Science and Technology, South Korea

Ghenadii Korotcenkov received his PhD in Physics and Technology of Semiconductor Materials and Devices from Technical University of Moldova in 1976 and his Dr. Sci. degree in Physics of Semiconductors and Dielectrics from Academy of Science of Moldova in 1990 (Highest Qualification Committee of the USSR, Moscow). He has more than 40-year experience as a teacher and scientific researcher. Long time he was a leader of gas sensor group and manager of various national and international scientific and engineering projects carried out in the Laboratory of Micro- and Optoelectronics, Technical University of Moldova. His research had financial support from International Foundations and Programs such as CRDF, MRDA, ICTP, INTAS, INCO-COPERNICUS, COST, NATO. 2007-2008 years he was an invited scientist in Korea Institute of Energy Research (Daejeon). Currently starting from 2008 year Dr. G. Korotcenkov is a research professor in the School of Materials Science and Engineering at Gwangju Institute of Science and Technology (GIST) in Korea.

Specialists from Former Soviet Union know G. Korotcenkov's research results in the field of study of Schottky barriers, MOS structures, native oxides, and photoreceivers on the basis of III-Vs compounds such as InP, GaP, AlGaAs, and InGaAs. His present scientific interests starting from 1995 year include material sciences, focusing on metal oxide film deposition and characterization, surface science, and design of thin film gas sensors and thermoelectric convertors. G. Korotcenkov is the author or editor of thirty five books and special issues, including 11 volume Chemical Sensors series published by Momentum Press (USA), 15 volume Chemical Sensors series published by Harbin Institute of Technology Press (China), 3 volume Porous Silicon: From Formation to Application issue published by CRC Press (USA) and 2 volume Handbook of Gas Sensor Materials published by Springer (USA). G. Korotcenkov is author and co-author of more than 550 scientific publications including twenty review papers, thirty five book chapters, more than 250 articles published in peer-reviewed scientific journals and more than 50 refereed papers published in international conference proceedings (h-factor = 38 (Scopus) and h = 44 (Google scholar citation)). He is a holder of 17 patents. He presented more than 200 reports on the National and International conferences, including fifteen invited talks. G. Korotcenkov was co-organizer of several International conferences. His research activities are honored by Award of the Supreme Council of Science and Advanced Technology of the Republic of Moldova (2004), The Prize of the Presidents of Ukrainian, Belarus and Moldovan Academies of Sciences (2003), Senior Research Excellence Award of Technical University of Moldova (2001, 2003, 2005), National Youth Prize of the Republic of Moldova in the field of science and technology (1980), among others. G. Korotcenkov also had Fellowship from International Research Exchange Board (IREX, USA, 1998), Brain Korea 21 Program (Korea, 2008-2012), and Brainpool Program (Korea, 2015-2017).

Preface to the series

Ghenadii Korotcenkov

The field of synthesis, study and application of metal oxides is one of the most rapidly progressing areas of science and technology. Metal oxides are one of the most ubiquitous compound groups on earth, which has large variety of chemical compositions, atomic structures, and crystalline shapes. In addition, metal oxides are known to possess unique functionalities that are absent or inferior in other solid materials. In particular, metal oxides represent an assorted and appealing class of materials, properties of which exhibit a full spectrum of electronic properties - from insulating to semiconducting, metallic, and superconducting. Moreover, almost all the known effects including superconductivity, thermoelectric effects, photoelectrical effects, luminescence and magnetism can be observed in metal oxides. Therefore, metal oxides have emerged as an important class of multifunctional materials with a rich collection of properties, which have great potential for numerous device applications. Specific properties of the metal oxides, such as the wide variety of materials with different electrophysical, optical, and chemical characteristics, their high thermal and temporal stability, and their ability to function in harsh environments, make metal oxides very suitable materials for designing transparent electrodes, high-mobility transistors, gas sensors, actuators, acoustical transducers, photovoltaic and photonic devices, photo- and heterogeneous catalysts, solid-state coolers, high-frequency and micromechanical devices, energy harvesting and storage devices, nonvolatile memories, and many others in the electronics, energy and health sectors. In these devices metal oxides can be successfully used as sensing or active layers, substrates, electrodes, promoters, structure modifiers, membranes and fibers, i.e. can be used as active and passive components.

Among other advantages of metal oxides are the low fabrication cost and robustness in practical applications. Furthermore, the metal oxides can be prepared in various forms such as ceramics, thick films and thin-film. At that for thin film deposition can be used deposition techniques that are compatible with standard microelectronic technology. Last factor is very important for large-scale production, because the microelectronic approach promotes low cost for mass production, offers the possibility of manufacturing devices on a chip, and guarantees good reproducibility. Various metal oxides nanostructures, including nanowires, nanotubes, nanofibers, core-shell structures and hollow nanostructures also can be synthesized. As it is known, the field of metal-oxide nanostructured morphologies (e.g., nanowires, nanorods, nanotubes, etc.) has become one of the most active research areas within the nanoscience community.

The ability to create a variety of metal oxide-based composites and the ability to synthesize various multi-component compounds significantly expand the range of properties that metal oxide-based materials can have, making metal oxides by a truly versatile multifunctional material for widespread use. As it is known small changes in their chemical composition and atomic structure can be accompanied by the spectacular variation in properties and behavior of metal oxides. Even now, advances in synthesizing and characterizing techniques are revealing numerous new functions of metal oxides.

Taking into account the importance of metal oxides for progress in microelectronics, optoelectronics, photonics, energy conversion, sensor and catalysis, a large number of various books devoted to this class of materials have been published. However, one should note that some books from this list are too general, some books are collections of various original works without any generalizations, and other ones were published many years ago. But, during past decade a great progress has been made on the synthesis as well as on the structural, physical, chemical characterization and application of metal oxides in various devices, and a large number of papers have been published on metal-oxides. In addition, till now many important topics related to metal oxides study and application have not been discussed. To remedy the situation in this area, we decided to generalize and systematize the results of research in this direction and to publish a series of books devoted to metal oxides.

One should note that proposed book series "Metal Oxides’ is the first one, devoted to consideration of metal oxides only. We believe that combining books on metal oxides in a series could help readers in searching required information on the subject. In particular, we plan that the books from our series, which have a clear specialization by its content, will provide interdisciplinary discussion for various oxide materials with a wide range of topics, from material synthesis and deposition to characterizations, processing and then to device fabrications and applications. This book series is prepared by a team of highly qualified experts, which guarantees it a high quality.

I hope that our books will be useful and comfortable in use. I would also like to hope that readers will consider this Metal Oxides book series like an encyclopedia of metal oxides that enables to understand the present status of metal oxides, to estimate the role of multifunctional metal oxides in design of advanced devices, and then based on observed knowledge to formulate new goals for the further research.

The intended audience of present book series is scientists and researchers, working or planning to work in the field of materials related to metal oxides, i.e. scientists and researchers whose activities are related to electronics, optoelectronics, energy, catalysis, sensors, electrical engineering, ceramics, biomedical designs, etc.. I believe that this Metal Oxides book series will also be interesting for practicing engineers or project managers in industries and national laboratories, which would like to design metal oxide-based devices, but don’t know how to do it, and how to select optimal metal oxide for specific applications. With many references to the vast resource of recently published literature on the subject, this book series will be serving as a significant and insightful source of valuable information, providing scientists and engineers with new insights for understanding and improving existing metal oxide-based devices and for designing new metal oxide-based materials with new and unexpected properties

I believe that this Metal Oxides book series would be very helpful for university students, post docs and professors. The structure of these books offers a basis for courses in the field of material sciences, chemical engineering, electronics, electrical engineering, optoelectronics, energy technologies, environmental control and many others. Graduate students could also find the book series to be very useful in their research and understanding features of metal oxides synthesis, study and application of this multifunctional material in various devices. We are sure that all of them will find information useful for their activity.

Finally, I thank all contributing authors and book editors who have been involved in the creation of these books. I am thankful that they agreed to participate in this project and for their efforts in the preparation of these books. Without their participation, this project would have not been possible. I also express my gratitude to Elsevier for giving us the opportunity to publish this series. I especially thank all team of editorial office at Elsevier for their patience during the development of this project and for encouraging us during the various stages of preparation.

1

Introduction

Adriana Zaleska-Medynska    University of Gdansk, Gdansk, Poland

1.1 Introduction

Nano- or microparticles of metal oxides irradiated by an appropriate light spectrum (in the ultraviolet and visible range) may serve as a source of active oxygen species as well as a source of photogenerated electrons and holes. These unique properties (so called photocatalytic properties) may be used in a wide range of environmental friendly processes, such as:

(1)pollutant degradation or removal from the gas and aqueous phases (water, wastewater and air treatment technologies);

(2)pollutant degradation at the surface of building materials (self-cleaning surfaces);

(3)conversion of solar energy into energy of chemical bonds (via water photosplitting or CO2 conversion into useful hydrocarbons);

(4)conversion of solar energy into electric energy (solar cells);

(5)photochemical transformation of specific chemical compounds.

Some undoubted advantages of the photocatalytic process are the ability to carry it out in ambient conditions of temperature and pressure, the possibility of using solar light to drive chemical reactions, and the possibility to reuse photocatalyst particles. Hydroxyl radicals, as well as other active oxygen species produced at the surface of irradiated metal oxide particles, could be a powerful and green oxidant employed to degrade organic pollutants and to remove inorganic compounds and microorganisms present in water, wastewater, or air. On the other hand, the mechanism of the photocatalytic process is quite complicated, the efficiency of most of the processes mentioned above is not too high at present, and moreover, the photoactivity of metal oxide particles is affected by a wide spectrum of factors. Notwithstanding this, the immense value of heterogeneous photocatalysis lies in its great potential to use solar energy to conduct chemical reactions and to convert solar energy into energy of chemical bonds. Efficient utilization of solar light for water splitting to generate hydrogen (clean energy carrier) and for artificial photosynthesis (CO2 photoconversion) seems to be a Holy Grail for the chemical community. Metal oxide photocatalysts could also be employed to produce energy via photoelectrochemical processes.

This book presents the principles and fundamentals of metal oxide-based heterogeneous photocatalysis and highlights the current developments and future potential of applications of unitary metal oxides, as well as their hybrids with noble metal nanoparticles and other semiconductors. The book consists of three main chapters, presenting the mechanisms of metal oxide-based photocatalysts excitation, the most important requirements for metal oxides used in photocatalysis, preparation methods of metal oxides used in photocatalysis, advantages, disadvantages, and achievements of the most important metal oxides (TiO2, WO3, ZnO, Fe2O3, Ta2O5, CuO) and the most important applications (water treatment, hydrogen production, air treatment, chemical synthesis, medical applications and applications in construction).

We hope that this book summarizes and organizes the knowledge in the field of metal-oxide based photocatalysis and that it can also be used in the classroom for undergraduate and graduate students focusing on heterogeneous photocatalysis, sustainable chemistry, energy conversion and storage, nanotechnology, chemical engineering, environmental protection, optoelectronics, sensors, and surface and interface science.

2

Fundamentals of metal oxide-based photocatalysis

Anna Gołąbiewska; Marek P. Kobylański; Adriana Zaleska-Medynska    University of Gdansk, Gdansk, Poland

Abstract

Photocatalysis is the change in the rate of reaction caused by light in the presence of a photocatalyst that absorbs light and is involved in the chemical transformation of the reactants. Heterogeneous photocatalysis is based mainly on semiconductor materials such as chalcogenides and metal oxides. Transition metal oxides and mixed oxides are the largest and most important groups of photocatalytic materials. This chapter discusses the photocatalytic reaction mechanisms of metal oxide semiconductors, the semiconductor bandgap structure, and the kinetics of photocatalysis.

Keywords

Heterogeneous photocatalysis; Metal oxides; Mechanism; Kinetics; Bandgap structure

2.1 Principles of metal oxide-based photocatalysis

The discovery of metal oxide-based photocatalysis was published in 1972 by Fujishima and Honda, who demonstrated that photoirradiation of a TiO2-covered electrode immersed in an aqueous electrolyte led to the production of O2 and H2 from TiO2 and Pl electrodes, respectively (so-called Honda-Fujishima effect) [1]. Notwithstanding this, some reports describing the ability of TiO2 particles to produce photocatalytic oxidation of organic compounds had been presented prior to this discovery. Thus, the ability of ZnO and TiO2 to generate photocatalytic degradation of organic compounds in the gas phase was announced in 1961 [2] and 1964 [3], respectively, and the photocatalytic oxidation of tetralin (1,2,3,4-tetrahydronaphthalene) in aqueous TiO2 suspension was reported in 1964 [4]. Since 1977, when Frank and Bard explored the possibility of employing TiO2 to decompose cyanide in aqueous suspension [5], there has been increasing interest in the environmental applications of such a process.

2.1.1 Mechanism of photocatalytic reactions

In contrast to metals, which possess a continuum of electronic states, semiconductors have an empty region in which there are no accessible energy levels that promote the recombination of an electron and a hole produced by photoactivation of a solid [6]. This empty region, which extends from the top of the filled valence band to the bottom of the vacant conduction band, is called the bandgap. Thus, the electronic structure of semiconductors is characterized by a filled valence band (VB) and an empty conduction band (CB). When a semiconductor is irradiated by a photon of energy hv that equals or surpasses the bandgap energy (Eg), an excited electron (e−) moves from the VB to the CB, leaving a hole (h+) behind (Eq. 2.1) [7]. The excited-state CB electrons and the VB holes can (1) recombine and be deactivated, (2) be trapped in metastable surface states, or (3) react with surrounding species.

In the absence of a suitable scavenger or a surface defect state, photogenerated charge carriers can recombine and be deactivated radiatively (release of light) or nonradiatively (release of heat) (Eq. 2.2). If a relevant scavenger or a surface defect state is available to trap the electron or hole, recombination is avoided and e−/h+ pairs can react with electron donors and electron acceptors adsorbed on the surface of the semiconductor or within the circumfluent electrical double layer of charged particles, as shown in Fig. 2.1. The VB holes are powerful oxidizers (+ 1.0 to + 3.5 V vs NHE [normal hydrogen electrode], depending on the semiconductor and pH) and the CB electrons are good reducers (+ 0.5 to − 1.5 V vs NHE) [8]. For TiO2 (the most used metal oxide in heterogeneous photocatalysis), the redox potential for photogenerated holes is + 2.53 V vs NHE (at pH 7), while the redox potential for CB electrons is − 0.52 V [9].

Fig. 2.1 Formation of active species at the surface of a semiconductor (photocatalysts) after light absorption ( hv  ≥  E g ): (i) initiation of an oxidative pathway of electron donors (D) by VB holes; (ii) initiation of a reductive pathway of electron acceptors (A) by CB electrons. Based on A.L. Linsebigler, G. Lu, J.T. Yates Jr, Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results, Chem. Rev. 95 (1995) 735–758; M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Environmental applications of semiconductor photocatalysis, Chem. Rev. 95 (1995) 69–96; M. Pelaez, N.T. Nolan, S.C. Pillai, M.K. Seery, P. Falaras, A.G. Kontos, P.S. Dunlop, J.W. Hamilton, J.A. Byrne, K. O'Shea, A review on the visible light active titanium dioxide photocatalysts for environmental applications, Appl. Catal. B Environ. 125 (2012) 331–349.

) (Eq. 2.3) that undergo further reactions to produce hydroxyl (•OH) radicals (Eqs. 2.5, 2.6), which are extremely powerful oxidants [10]. Meanwhile, positive holes oxidize OH− or H2O at the semiconductor surface to produce •OH radicals (Eqs. 2.4, 2.8, reprinted from [11]). Afterwards, the •OH radicals oxidize organic compounds (e.g., organic pollutants) resulting in their mineralization and the formation of CO2, H2O, and eventually simple inorganic compounds containing heteroatoms (Eq. 2.9, reprinted from [11]).

   (2.1)

   (2.2)

   (2.3)

   (2.4)

   (2.5)

   (2.6)

   (2.7)

   (2.8)

(2.9)

; E⁰ (OH•, H+/H2O) = 2.31 V vs NHE) [12].

The ability of a semiconductor to undergo the transfer of photoinduced electrons to adsorbed species on its surface is a function of the positions of the CB and VB edges and the redox potential of the adsorbate. The potential level of the acceptor molecules or species thermodynamically has to be placed below (i.e., more positive than) the lower edge of the semiconductor CB. The potential level of the donor has to be located higher than (i.e., more negative than) the upper edge of the semiconductor VB to be able to provide an electron to the vacant hole. The correlation between the band-edge positions of the TiO2 photocatalyst and the relevant redox couples at pH 7 is summarized in Fig. 2.2, while the value of the bandgap and the band-edge positions for the most common metal oxides are presented in Section 2.2 (Table 2.4.).

Fig. 2.2 Potentials for various redox processes that occur on the surface of TiO 2 at pH 7. Reproduced with permission from J. Kou, C. Lu, J. Wang, Y. Chen, Z. Xu, R.S. Varma, Selectivity enhancement in heterogeneous photocatalytic transformations, Chem. Rev. 117 (2017) 1445–1514.

For hydrogen production (in a water-splitting process), the bottom level of the CB should be more negative than the reduction potential of H+/H2 (0 V vs NHE), while the top level of the VB should be more positive than the oxidation potential of O2/H2O (1.23 V) for efficient hydrogen and oxygen production from water by photocatalysis, as shown in Fig. 2.3. Even the band-edge positions of TiO2 are suitable for water photodecomposition, where only TiO2 becomes inactive because of the presence of a large overpotential for the production of H2 and O2 on the surface of TiO2 [6].

Fig. 2.3 Mechanism of photocatalytic water splitting for hydrogen production over semiconductor particles. Based on M. Ni, M.K.H. Leung, D.Y.C. Leung, K. Sumathy, A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production, Renew. Sust. Energy Rev. 11 (2007) 401–425.

Linsebigler et al. indicated that maintained photodecomposition of water in the presence of TiO2 is possible under the following experimental conditions [6]:

1.Use of a photoelectrochemical cell with a TiO2 anode and a metal cathode (e.g., Pt) and a small, externally applied electrical potential (> 0.25 V) [6]. In this system, the photoexcitation of TiO2 pumps electrons from its VB into its CB. The electrons then move through the external circuit to the Pt cathode where H2 is produced, while O2 is formed on the TiO2.

2.Use of TiO2 powder modified by metal nanoparticles (e.g., Pt) for H2 generation and by metal oxide particles (e.g., RuO2) for O2 production. In this system, irradiation of TiO2 results in the injection of electrons into the Pt particles and holes into the RuO2 particles. The trapped charges reduce water to hydrogen at the Pt surface and the trapped holes oxidize water to oxygen at the RuO2 surface due to a significant reduction in the overpotential for H2 and O2 formation by the presence of Pt and RuO2, respectively.

3.Introduction into the reaction environment of a sacrificial species, which removes one of the formed products and results in the shift of the reaction equilibrium toward further water photosplitting. Thus, it could be predicted that if the sacrificial agent is oxidized by the product from the reaction with holes (e.g., O2), maintained H2 production will be observed [6].

The efficiency of converting solar energy to hydrogen (i.e., photocatalytic water-splitting) on a single semiconductor is still limited owing to the following reasons [66]:

1.Quick back reaction between photogenerated e−/h+ pairs: CB electrons can react with VB holes followed by energy release (via radiative or nonradiative decay);

2.Backward reaction: splitting of water molecules into hydrogen and oxygen increases energy, so the backward reaction, i.e., the recombination of hydrogen and oxygen into water, proceeds easily;

3.Limited number of metal oxides excited by visible light: The bandgap of most stable semiconductors (e.g., TiO2) is greater than 3.2 eV, so only ultraviolet (UV) light can be utilized for hydrogen production. The solar spectrum reaching ground level contains only about 4% of UV light and about 50% of visible light. Thus, the inability to absorb light from the visible region limits the efficiency of solar-driven photocatalysis to produce hydrogen [66].

Titanium dioxide has high photostability, is chemically inert, and has relatively high oxidation efficiency under UV light (λ < 387 nm), the energy of which exceeds the TiO2 bandgap (from 3.0 to 3.2 eV for the rutile and anatase forms, respectively). This makes TiO2 a very popular and commonly used semiconductor in heterogeneous photocatalysis. However, the application of metal oxide-based photocatalysis on a large scale requires photocatalysts with high reactivity under visible light (λ > 400 nm) to be able to use renewable solar energy. The five main approaches to forcing photocatalytic activity from wide-bandgap semiconductors (e.g., TiO2) under visible light irradiation are (1) doping, (2) sensitization, (3) charge transfer complex formation, (4) coupling with a narrow-bandgap semiconductor, and (5) addition of noble metal nanoparticles.

According to the Kisch classification, metal oxide-based photocatalysis has two reaction modes: direct and indirect [67]. In direct photocatalysis, light excitation (hv) results in the generation of an e−/h+ pair localized at the semiconductor surface, followed by the two interfacial electron transfer (IFET) reactions with donor and acceptor species (Figs. 2.1 and 2.3). In indirect photocatalysis, electrons or holes that appear at the surface of the semiconductor originate from an adsorbed molecule (e.g., semiconductor photosensitization).

2.1.1.1 Doped semiconductors

The activity of a doped semiconductor under visible light is due to a new energy level produced in the bandgap of the semiconductor by the dispersion of dopant atoms (cations or anions) in the crystal structure of the semiconductor (Fig. 2.4). Transition metals, rare earth metals, noble metals, and poor metals can be used for cation doping.

Fig. 2.4 Mechanism of visible light-induced excitation through the metal- or nonmetal-doped wide-bandgap semiconductor.

Doping with transition metals tunes the electronic structure and shifts the light absorbed from UV to visible light, thus improving the photocatalytic activity of wide-bandgap semiconductors. The observed redshift is caused by the charge transfer between the d electrons and the CB or the VB of the semiconductor. The transition metal creates a new electron state inside the electronic structure of the wide-bandgap semiconductor by capturing the excited electrons from the VB of the semiconductor and preventing the recombination of charge carriers [63]. As metal ions are incorporated into the TiO2 lattice, impurity energy levels are formed in the bandgap of TiO2, as indicated by Eqs. 2.10, 2.11 [66]:

   (2.10)

   (2.11)

where M and Mn + represent metal and metal ion dopant, respectively. The energy level of Mn +/M(n − 1)+ should be less negative than that of the CB edge of TiO2, while the energy level of Mn +/M(n + 1)+ should be less positive than that of the VB edge of TiO2 [66].

Depending on the redox energy state of the doping transition metal, the substitution of metal ions into the TiO2 (or other metal oxide) introduces an intraband state close to the CB or VB edge, inducing visible light absorption at subbandgap energies [68]. The additional benefit of doping with transition metal is the enhanced trapping of electrons, which inhibits the recombination of electrons and holes during illumination [6]. However, the type of transition metal, its content, and the microstructural characteristics of the metal oxide are the main factors which affect the effectiveness of the photodegradation of miscellaneous compounds induced by visible light irradiation [63,69,70].

The next popular approach for changing the optical response of the semiconductor to visible light is to dope with anionic nonmetals, such as N, C, S, B, P, and I [71]. Compared to doping with cations, the role of nonmetallic anions as recombination centers might be minimized. For nonmetal-doped TiO2, the impurity states are near the VB edge but do not act as charge carriers. Both theoretical [72] and experimental [73] studies revealed that for N-doped TiO2, the N 2p localized states were just above the top of the O 2p VB.

However, the oxidation power and mobility of photogenerated holes in the electronic state of isolated N are lower than those in the VB of TiO2. Thus, in the case of N-doped TiO2, superoxide radicals are responsible for organic compound decomposition rather than OH radicals [74]. Doping by S, C, and P also induces mid-bandgap levels leading to visible light absorption. Doping with F does not shift the TiO2 bandgap but it does enhance surface acidity and cause formation of reduced Ti³ + ions owing to the charge compensation between F− and Ti⁴ +.

2.1.1.2 Semiconductor photosensitization

In semiconductor photosensitization, photoexcited electrons or holes appear in the CB or the VB of the semiconductor, respectively, from the excited state of organic molecules adsorbed on the surface of the semiconductor. This type of photoinduced electron transfer is considered a weak-type interaction between a semiconductor band and the surface molecule and is known as the Sakata-Hiramoto-Hashimoto (SHH) mechanism [75] (Fig. 2.5). According to the SHH model, photosensitization results from photoinduced electron transfer and depends on the type of semiconductor [76]. In n-type semiconductors, electrons are injected into the CB, with possible contribution of the empty surface state (Fig. 2.5A). When the energy of the highest occupied molecular orbital (HOMO) of the photosensitizer is sufficiently low, hole injection into the VB of a p-type semiconductor is observed (Fig. 2.5B).

Fig. 2.5 Energy diagrams showing indirect photosensitization of (A) n- and (B) p-type semiconductors according to the SHH mechanism: (A) under photoexcitation of an adsorbed dye, electrons are transferred from the excited dye to the CB of the semiconductor; (B) under photoexcitation of the adsorbed dye, holes are injected from the excited dye to the VB of the semiconductor. Based on T. Sakata, K. Hashimoto, M. Hiramoto, New aspects of electron transfer on semiconductor surface: dye-sensitization system, J. Phys. Chem. 94 (1990) 3040–3045; W. Macyk, K. Szaciłowski, G. Stochel, M. Buchalska, J. Kuncewicz, P. Łabuz, Titanium(IV) complexes as direct TiO2 photosensitizers, Coord. Chem. Rev. 254 (2010) 2687–2701.

and the hydrogen peroxide radical •OOH. These reactive species can also be disproportionate to yield the hydroxyl radical •OH (Fig. 2.6A). In addition to the above-mentioned species, ¹O2 can also be formed under some reaction conditions. Oxygen has two singlet excited states above the triplet ground states. This makes ³O2 an efficient quencher for almost all other excited states. ¹O2 is produced by quenching the excited state of the photosensitizer with ³O2, as summarized in Eqs. 2.12, 2.13, where S refers to the photosensitizer.

   (2.12)

   (2.13)

Fig. 2.6 Indirect photosensitization: (A) formation of oxygen active species at the surface of the photosensitized semiconductor; (B) formation of hydrogen at the surface of the photosensitized semiconductor (dye-mediated water splitting). Based on S.G. Kumar, L.G. Devi, Review on modified TiO2 photocatalysis under UV/visible light: selected results and related mechanisms on interfacial charge carrier transfer dynamics, J. Phys. Chem. A 115 (2011) 13211–13241.

The subsequent radical chain reaction leads to the degradation of the dye. The time for electron injection between the semiconductor and the adsorbate depends on the nature of the sensitizer, the semiconductor, and their interaction [11]. Some frequently used dyes and their absorption wavelength maxima are listed in Table 2.1.

Table 2.1

Modified from M. Ni, M.K.H. Leung, D.Y.C. Leung, K. Sumathy, A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production, Renew. Sust. Energy Rev. 11 (2007) 401–425; A.R. Khataee, M.B. Kasiri, Photocatalytic degradation of organic dyes in the presence of nanostructured titanium dioxide: Influence of the chemical structure of dyes, J. Mol. Catal. A Chem. 328 (2010) 8–26; N.A. Ludin, A.M. Al-Alwani Mahmoud, A. Bakar Mohamad, A.A.H. Kadhum, K. Sopian, N.S. Abdul Karim, Review on the development of natural dye photosensitizer for dye-sensitized solar cells, Renew. Sust. Energy Rev. 31 (2014) 386–396.

2.1.1.3 Charge transfer interaction

Another way to modify a wide-bandgap semiconductor (such as TiO2) for visible light absorption is the formation of a charge transfer (CT) complex between the semiconductor and the surface adsorbate, neither of which absorbs visible light [77–81]. The mechanism of CT complex-mediated visible light excitation is different from that of common dye photosensitization. In CT sensitization, the electron is photoexcited directly from the ground-state adsorbate to the CB of the semiconductor, without the involvement of the excited state of the adsorbate.

The strong interaction between the semiconductor CB and a surface molecule can be represented by the Creutz-Brunschwig-Sutin model [82–84]. For strong electronic coupling, the interaction between a ligand and the surface of the semiconductor results in the formation of a surface coordination species (Fig. 2.7A and B). New energy levels are formed with the appropriate arrangement of molecular orbitals. For an n-type semiconductor (Fig. 2.7A), a bonding orbital is created via interaction of the HOMO level of the surface ligand with the empty surface state. Typically, the resulting surface state, with HOMO and LUMO characteristics, is situated at the surface ligand (electron donor) and constitutes a part of the CB. In this case, excitation of the surface complex leads to optical electron transfer from the surface molecule to the CB. The opposite occurs when the p-type semiconductor interacts with the electron acceptor (Fig. 2.7B).

Fig. 2.7 Energy diagrams showing direct photosensitization of (A) n- and (B) p-type semiconductors according to the Creutz-Brunschwig-Sutin model (LMCT: ligand-to-metal charge transfer; MLCT: metal-to-ligand charge transfer; E g : bandgap energy; E F : Fermi level). Based on T. Sakata, K. Hashimoto, M. Hiramoto, New aspects of electron transfer on semiconductor surface: dye-sensitization system, J. Phys. Chem. 94 (1990) 3040–3045; W. Macyk, K. Szaciłowski, G. Stochel, M. Buchalska, J. Kuncewicz, P. Łabuz, Titanium(IV) complexes as direct TiO2 photosensitizers, Coord. Chem. Rev. 254 (2010) 2687–2701.

The simple surface complexes of TiO2 have three basic structures: (1) monodentate structure with the organic ligands engaging one coordination site of TiO2, (2) bidentate chelating structure with the ligand occupying two coordination sites, and (3) bidentate bridging structure composed of a chelating ligand binding two neighboring Ti centers. The bidentate surface complexes form only if