Photocatalysis

In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalysed photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the photocatalytic activity (PCA) depends on the ability of the catalyst to create electron–hole pairs, which generate free radicals (e.g. hydroxyl radicals: •OH) able to undergo secondary reactions. Its practical application was made possible by the discovery of water electrolysis by means of titanium dioxide. The commercially used process is called the advanced oxidation process (AOP). There are several ways the AOP can be carried out; these may (but do not necessarily) involve TiO₂ or even the use of UV light. Generally the defining factor is the production and use of the hydroxyl radical.

In the experiment above, photons from a light source (out of frame on the right hand side) are absorbed by the surface of the titanium dioxide disc, exciting electrons within the material. These then react with the water molecules, splitting it into its constituents of hydrogen and oxygen. In this experiment, chemicals dissolved in the water prevent the formation of oxygen, which would otherwise recombine with the hydrogen.

Types of photocatalysis

Homogeneous photocatalysis

In homogeneous photocatalysis, the reactants and the photocatalysts exist in the same phase. The most commonly used homogeneous photocatalysts include ozone and photo-Fenton systems (Fe⁺ and Fe⁺/H₂O₂). The reactive species is the •OH which is used for different purposes. The mechanism of hydroxyl radical production by ozone can follow two paths.^[1]

O₃ + hν → O₂ + O(1D) (? O₃ "-" hν → O₂ + O(1D) ?)

O(1D) + H₂O → •OH + •OH

O(1D) + H₂O → H₂O₂

H₂O₂ + hν → •OH + •OH

Similarly, the Fenton system produces hydroxyl radicals by the following mechanism^[2]

Fe²⁺ + H₂O₂→ HO• + Fe³⁺ + OH⁻

Fe³⁺ + H₂O₂→ Fe²⁺ + HO•2 + H⁺

Fe²⁺ + HO• → Fe³⁺ + OH⁻

In photo-Fenton type processes, additional sources of OH radicals should be considered: through photolysis of H₂O₂, and through reduction of Fe³⁺ ions under UV light:

H₂O₂ + hν → HO• + HO•

Fe³⁺ + H₂O + hν → Fe²⁺ + HO• + H⁺

The efficiency of Fenton type processes is influenced by several operating parameters like concentration of hydrogen peroxide, pH and intensity of UV. The main advantage of this process is the ability of using sunlight with light sensitivity up to 450 nm, thus avoiding the high costs of UV lamps and electrical energy. These reactions have been proven more efficient than the other photocatalysis but the disadvantages of the process are the low pH values which are required, since iron precipitates at higher pH values and the fact that iron has to be removed after treatment.

Heterogeneous photocatalysis

Heterogeneous catalysis has the catalyst in a different phase from the reactants. Heterogeneous photocatalysis is a discipline which includes a large variety of reactions: mild or total oxidations, dehydrogenation, hydrogen transfer, ¹⁸O₂–¹⁶O₂ and deuterium-alkane isotopic exchange, metal deposition, water detoxification, gaseous pollutant removal, etc.

Most common heterogeneous photocatalysts are transition metal oxides and semiconductors, which have unique characteristics. Unlike the metals which have a continuum of electronic states, semiconductors possess a void energy region where no energy levels are available to promote recombination of an electron and hole produced by photoactivation in the solid. The void region, which extends from the top of the filled valence band to the bottom of the vacant conduction band, is called the band gap.^[3] When a photon with energy equal to or greater than the materials band gap is absorbed by the semiconductor, an electron is excited from the valence band to the conduction band, generating a positive hole in the valence band. The excited electron and hole can recombine and release the energy gained from the excitation of the electron as heat. Recombination is undesirable and leads to an inefficient photocatalyst. The ultimate goal of the process is to have a reaction between the excited electrons with an oxidant to produce a reduced product, and also a reaction between the generated holes with a reductant to produce an oxidized product. Due to the generation of positive holes and electrons, oxidation-reduction reactions take place at the surface of semiconductors. In the oxidative reaction, the positive holes react with the moisture present on the surface and produce a hydroxyl radical.

Oxidative reactions due to photocatalytic effect:

UV + MO → MO (h + e⁻)

Here MO stands for metal oxide ---

h⁺ + H₂O → H⁺ + •OH

2 h⁺ + 2 H₂O → 2 H⁺ + H₂O₂

H₂O₂→ HO• + •OH

The reductive reaction due to photocatalytic effect:

e⁻ + O₂ → •O₂⁻

•O₂− + HO•2 + H⁺ → H₂O₂ + O₂

HOOH → HO• + •OH

Ultimately, the hydroxyl radicals are generated in both the reactions. These hydroxyl radicals are very oxidative in nature and non selective with redox potential of (E₀ = +3.06 V)^[4]

Applications

• Conversion of water to hydrogen gas by photocatalytic water splitting.^[5] An efficient photocatalyst in the UV range is based on a sodium tantalite (NaTaO₃) doped with La and loaded with a cocatalyst nickel oxide. The surface of the sodium tantalite crystals is grooved with so called nanosteps that is a result of doping with lanthanum (3–15 nm range, see nanotechnology). The NiO particles which facilitate hydrogen gas evolution are present on the edges, with the oxygen gas evolving from the grooves.
• Use of titanium dioxide in self-cleaning glass. Free radicals^[6][7] generated from TiO₂ oxidize organic matter.^[8][9]
• Disinfection of water by supported titanium dioxide photocatalysts, a form of solar water disinfection (SODIS).^[10][11]
• Use of titanium dioxide in self-sterilizing photocatalytic coatings (for application to food contact surfaces and in other environments where microbial pathogens spread by indirect contact).^[12]
• Oxidation of organic contaminants using magnetic particles that are coated with titanium dioxide nanoparticles and agitated using a magnetic field while being exposed to UV light.^[13]
• Conversion of carbon dioxide into gaseous hydrocarbons using titanium dioxide in the presence of water.^[14] As an efficient absorber in the UV range, titanium dioxide nanoparticles in the anatase and rutile phases are able to generate excitons by promoting electrons across the band gap. The electrons and holes react with the surrounding water vapor to produce hydroxyl radicals and protons. At present, proposed reaction mechanisms usually suggest the creation of a highly reactive carbon radical from carbon monoxide and carbon dioxide which then reacts with the photogenerated protons to ultimately form methane. Although the efficiencies of present titanium dioxide based photocatalysts are low, the incorporation of carbon based nanostructures such as carbon nanotubes^[15] and metallic nanoparticles^[16] have been shown to enhance the efficiency of these photocatalysts.
• Sterilization of surgical instruments and removal of unwanted fingerprints from sensitive electrical and optical components.^[17]
• A less-toxic alternative to tin and copper-based antifouling marine paints, ePaint, generates hydrogen peroxide by photocatalysis.
• Decomposition of crude oil with TiO₂ nanoparticles: by using titanium dioxide photocatalysts and UV-A radiation from the sun, the hydrocarbons found in crude oil can be turned into H₂O and CO₂. Higher amounts of oxygen and UV radiation increased the degradation of the model organics. These particles can be placed on floating substrates, making it easier to recover and catalyze the reaction. This is relevant since oil slicks float on top of the ocean and photons from the sun target the surface more than the inner depth of the ocean. By covering floating substrates like woodchips with epoxy adhesives, water logging can be prevented and TiO₂ particles can stick to the substrates. With more research, this method should be applicable to other organics.
• Decontamination of water with photocatalysis and adsorption: the removal and destruction of organic contaminants in groundwater can be addressed through the impregnation of adsorbents with photoactive catalysts. These adsorbents attract contaminating organic atoms/molecules like tetrachloroethylene to them. The photoactive catalysts impregnated inside speed up the degradation of the organics. Adsorbents are placed in packed beds for 18 hours, which would attract and degrade the organic compounds. The spent adsorbents would then be placed in regeneration fluid, essentially taking away all organics still attached by passing hot water counter-current to the flow of water during the adsorption process to speed up the reaction. The regeneration fluid then gets passed through the fixed beds of silica gel photocatalysts to remove and decompose the rest of the organics left. Through the use of fixed bed reactors, the regeneration of adsorbents can help increase the efficiency.
• Decomposition of polyaromatic hydrocarbons (PAHs). Triethylamine (TEA) was utilized to solvate and extract the polyaromatic hydrocarbons (PAHs) found in crude oil. By solvating these PAHs, TEA can attract the PAHs to itself. Once removed, TiO₂ slurries and UV light can photocatalytically degrade the PAHs. The figure shows the high success rate of this experiment. With high yielding of recoveries of 93–99% of these contaminants, this process has become an innovative idea that can be finalized for actual environmental usage. This procedure demonstrates the ability to develop photocatalysts that would be performed at ambient pressure, ambient temperature, and at a cheaper cost.

Quantification of Photocatalytic Activity

ISO 22197 -1:2007 specifies a test method for the determination of the nitric oxide removal performance of materials that contain a photocatalyst or have photocatalytic films on the surface.^[18]

Specific FTIR systems are used to characterise photocatalytic activity and/or passivity especially with respect to Volatile Organic Compounds VOCs and representative matrices of the binders applied.^[19]

Recent studies show that mass spectrometry can be a powerful tool to determine photocatalytic activity of certain materials by following the decomposition of gaseous pollutants such as nitrogen oxides or carbon dioxide ^[20]

See also

• Photoelectrochemical cell
• Photolysis
• Photocatalytic water splitting
• Photoredox catalysis

References

1. Wu, CH; Chang, CL (2006). "Decolorization of Reactive Red 2 by advanced oxidation processes: Comparative studies of homogeneous and heterogeneous systems". Journal of hazardous materials 128 (2–3): 265–72. doi:10.1016/j.jhazmat.2005.08.013. PMID 16182444.
2. Peternel, IT; Koprivanac, N; Bozić, AM; Kusić, HM (2007). "Comparative study of UV/TiO2, UV/ZnO and photo-Fenton processes for the organic reactive dye degradation in aqueous solution". Journal of hazardous materials 148 (1–2): 477–84. doi:10.1016/j.jhazmat.2007.02.072. PMID 17400374.
3. Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T. (1995). "Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results". Chemical Reviews 95 (3): 735–758. doi:10.1021/cr00035a013.
4. Daneshvar, N; Salari, D; Khataee, A.R (2004). "Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2". Journal of Photochemistry and Photobiology A: Chemistry 162 (2–3): 317–322. doi:10.1016/S1010-6030(03)00378-2.
5. Kudo, Akihiko; Kato, Hideki; Tsuji, Issei (2004). "Strategies for the Development of Visible-light-driven Photocatalysts for Water Splitting". Chemistry Letters 33 (12): 1534. doi:10.1002/chin.200513248.
6. "Snapcat Photo Catalytic Oxidation with Titanium Dioxide (2005)". CaluTech UV Air. Retrieved 2006-12-05.
7. Kondrakov AO, Ignatev AN, Lunin VV, Frimmel FH, Braese S, Horn H (2016). "Roles of water and dissolved oxygen in photocatalytic generation of free OH radicals in aqueous TiO₂ suspensions: An isotope labeling study". Applied Catalysis B: Environmental 182: 424–430. doi:10.1016/j.apcatb.2015.09.038.
8. "Photocatalysis Applications of Titanium Dioxide TiO₂". Titanium Information. titaniumart.com.
9. Kondrakov AO, Ignatev AN, Frimmel FH, Braese S, Horn H, Revelsky AI (2014). "Formation of genotoxic quinones during bisphenol A degradation by TiO₂ photocatalysis and UV photolysis: A comparative study". Applied Catalysis B: Environmental 160: 106–114. doi:10.1016/j.apcatb.2014.05.007.
10. McCullagh C, Robertson JMC, Bahnemann DW, Robertson PKJ (2007). "The application of TiO₂ photocatalysis for disinfection of water contaminated with pathogenic micro-organisms: a review". Research on Chemical Intermediates 33 (3–5): 359–375. doi:10.1163/156856707779238775.
11. Hanaor, Dorian A. H.; Sorrell, Charles C. (2014). "Sand Supported Mixed-Phase TiO₂ Photocatalysts for Water Decontamination Applications". Advanced Engineering Materials 16 (2): 248–254. doi:10.1002/adem.201300259.
12. Cushnie TPT, Robertson PKJ, Officer S, Pollard PM, Prabhu R, McCullagh C, Robertson JMC (2010). "Photobactericidal effects of TiO₂ thin films at low temperature". Journal of Photochemistry and Photobiology A: Chemistry 216 (2-3): 290–294. doi:10.1016/j.jphotochem.2010.06.027.
13. Kostedt IV, William L.; Jack Drwiega; David W. Mazyck; Seung-Woo Lee; Wolfgang Sigmund; Chang-Yu Wu; Paul Chadik (2005). "Magnetically agitated photocatalytic reactor for photocatalytic oxidation of aqueous phase organic pollutants". Environmental Science & Technology (American Chemical Society) 39 (20): 8052–8056. doi:10.1021/es0508121.
14. Tan, S. S.; L. Zou; E. Hu (2006). "Photocatalytic reduction of carbon dioxide into gaseous hydrocarbon using TiO₂ pellets". Catalysis Today 115: 269–273. doi:10.1016/j.cattod.2006.02.057.
15. Yao, Y. Yao; G. Li; S. Ciston; R. M. Lueptow; K. Gray (2008). "Photoreactive TiO₂/Carbon Nanotube Composites: Synthesis and Reactivity". Environmental Science & Technology (American Chemical Society) 42 (13): 4952–4957. doi:10.1021/es800191n.
16. Linsebigler, A. L.; G. Lu; J.T. Yates (1995). "Photocatalysis on TiO₂ Surfaces: Principles, Mechanisms, and Selected Results". Chemical Reviews 95 (3): 735–758. doi:10.1021/cr00035a013.
17. Science News
18. ISO 22197-1:2007
19. Unique Gas Analyser Helps to Characterize Photoactive Pigments
20. Manuel Nuño, Richard J. Ball and Chris R. Bowen. "Study of solid/gas phase photocatalytic reactions by electron ionization mass spectrometry" J Mass Spec, 2014, 49 (8), p. 716-726