Investigation of Advanced Oxidation Process in the Presence of TiO2 Semiconductor as Photocatalyst: Property, Principle, Kinetic Analysis, and Photocatalytic Activity
Abstract
:1. Introduction
2. Photocatalysis
2.1. Principles
- Absorption of photons with equal/larger energy than the bandgap energy of semiconductor under irradiation of light that results in the photogeneration of electron and hole pairs;
- Charge carrier separation;
- Transfer of charge carriers to the surface of semiconducting material;
- Redox reactions initiated by charge carriers.
- Transfer of the pollutants from the liquid phase to the surface of catalyst;
- Pollutants adsorption onto the surface of the activated catalyst;
- Photogeneration of ROSs, including •OH, followed by pollutants degradation;
- Desorption of intermediates from the surface of catalyst;
- Transferring intermediates into the liquid phase.
2.2. Kinetic Analysis
- Adsorption–desorption equilibrium of substrate species is not disturbed under illumination (as a pre-assumption);
- Ambiguous photon flow intervention (as an experimental parameter);
- Issues in intervening physical meaning;
- Chemical nature of the semiconductor surface does not change during photocatalysis (as a pre-assumption);
- Disregarding the electronic interaction of surface with substrate species;
- Considering that chemisorption of organic species onto the surface of catalyst is vital for photocatalysis.
3. Band Gap Estimation and Quantum Size Effect
- For direct allowed transitions: n = 1/2;
- For indirect allowed transitions: n = 2;
- For direct forbidden transitions: n = 3/2;
- For indirect forbidden transitions: n = 3.
4. TiO2
4.1. General Properties and Applications
4.2. Optical and Electrical Properties of TiO2
4.3. Promising Phases of TiO2 for Photocatalytic Applications
4.4. Photocatalytic Activity of Anatase Titania Compared with Its Other Polymorphs
4.5. Colorful TiO2 versus White TiO2
5. Conclusions and Perspectives
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Type of Primary Reaction | Primary Reaction | Characteristic Time (s) |
---|---|---|
Generation of charge carriers | TiO2 + hυ → ecb− + hvb+ | fs |
Charge carrier trap** | Hvb+ + > TiIVOH → > {TiIVOH}+ | 10 ns |
| ecb− + > TiIV → >TiIII | 10 ns |
| ecb− + > TiIVOH ↔ {>TiIIIOH} | 100 ps |
Charge carrier recombination | hvb+ + {> TiIIIOH} → >TiIVOH ecb− + > {TiIVOH•}+ → >TiIVOH | 10 ns 100 ns |
Interfacial charge transfer | {>TiIVOH•}+ + Red → > TiIVOH + Red•+ etr− + OX → TiIVOH + OX•− | 100 ns ms |
Properties | TiO2 Nanostructures | ||
---|---|---|---|
Rutile | Anatase | Brookite | |
Crystal Structure | Tetragonal | Tetragonal | Orthorhombic |
Lattice constant (A) | a = 4.5936 c =2.9587 | a = 3.784 c = 9.515 | a = 9.184 b = 5.447 c = 5.154 |
Molecule (cell) | 2 | 2 | 4 |
Volume/molecule (A˚3) | 31.21 | 34.061 | 32.172 |
Density (g cm−3) | 4.13 | 3.79 | 3.99 |
Ti–O bond length () | 1.949 (4) 1.980 (2) | 1.937 (4) 1.965 (2) | 1.87–2.04 |
O–Ti–O bond angle | |||
Band gap at 10 K | 3.051 eV | 3.46 eV | |
Static dielectric constant (ε0, in MHz range) | 173 | 48 | |
High frequency dielectric constant, () | 8.35 | 6.25 |
Synthesis Method | Light Source | Improvement of Photocatalytic Activity | Improvement of Photoelectrochemical Properties | References |
---|---|---|---|---|
Melted aluminum reduction of pristine anodized and air-annealed TiO2 nanotube arrays | The simulated sunlight (intensity of 100 mW cm−2) | - | Approximately 5 times higher than pristine TiO2 nanotube arrays | [187] |
Electrospinning process | A 150 W xenon lamp | - | Approximately a 10-fold increase compared with pristine TiO2 nanofibers | [188] |
In situ plasma hydration of TiO2 thin films | A 150 W xenon lamp (intensity of 100 mW cm−2) | - | Approximately 2.5 times higher than pristine TiO2 thin films | [189] |
Electrochemical reductive do** |
| - | Approximately 2.2 times higher than pristine anodic TiO2 nanotubes (under both UV and simulated solar irradiation) | [190] |
Using Ti2O3 as precursor for preparing Ti3+ self-doped TiO2 nanowires | A 20 W UV lamp | Approximately 7.5 times higher than pure TiO2 (P25) in photodegradation of methyl orange | - | [191] |
hydrogen plasma assisted chemical vapour deposition | A 50 W simulated solar light source | Complete photodegradation of rhodamine B after approximately 30 min against partial photodegradation of rhodamine B even after 50 min for pure TiO2 | - | [192] |
Annealing the TiO2 nanobelts in hydrogen atmosphere |
|
| - | [193] |
Annealing the TiO2 nanobelts in hydrogen atmosphere | A 300 W xenon arc lamp | - | Approximately 9.2 times higher than pristine TiO2 nanobelts | [193] |
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Navidpour, A.H.; Abbasi, S.; Li, D.; Mojiri, A.; Zhou, J.L. Investigation of Advanced Oxidation Process in the Presence of TiO2 Semiconductor as Photocatalyst: Property, Principle, Kinetic Analysis, and Photocatalytic Activity. Catalysts 2023, 13, 232. https://doi.org/10.3390/catal13020232
Navidpour AH, Abbasi S, Li D, Mojiri A, Zhou JL. Investigation of Advanced Oxidation Process in the Presence of TiO2 Semiconductor as Photocatalyst: Property, Principle, Kinetic Analysis, and Photocatalytic Activity. Catalysts. 2023; 13(2):232. https://doi.org/10.3390/catal13020232
Chicago/Turabian StyleNavidpour, Amir Hossein, Sedigheh Abbasi, Donghao Li, Amin Mojiri, and John L. Zhou. 2023. "Investigation of Advanced Oxidation Process in the Presence of TiO2 Semiconductor as Photocatalyst: Property, Principle, Kinetic Analysis, and Photocatalytic Activity" Catalysts 13, no. 2: 232. https://doi.org/10.3390/catal13020232