Abstract
The ABCs of empirical chemical kinetics are highlighted from the scratch. Aspects of dynamics regarding charge carrier trapping and recombination are essential part of this discussion. The effect of imposition of external constrains such as temperature of the reactivity solution, concentration of the subject compound, intensity and wavelength of light on photocatalytic degradation system is emphasised. Because of the crucial position of light intensity in heterogeneous photocatalysis, the principles of operation of important chemical actinometric systems are presented.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Aguado J, Grieken R van, López-Munõz M-J et al (2006) A comprehensive study of the synthesis, characterization and activity of TiO2 and mixed TiO2/SiO2 photocatalysts. Appl Catal A 312:202–212
Arańa J, Nieto JLM, Melián JAH (2004) Photocatalytic degradation of formaldehyde containing wastewater from veterinarian laboratories. Chemosphere 55:893–904
Augugliaro V, Kisch H, Loddo V et al (2008) Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home-prepared titanium dioxide 1. Selectivity enhancement by aliphatic alcohols. Appl Catal A 349:182–188
Bahnemann DW, Hilgendorff M, Memming R (1997) Charge carrier dynamics at TiO2 particles: reactivity of free and trapped holes. J Phys Chem B 101:4265–4275
Bauer C, Boschloo G, Mukhtar E et al (2004) Ultrafast relaxation dynamics of charge carriers relaxation in ZnO nanocrystalline thin films. Chem Phys Lett 387:176–181
Bayarri B, Abellán MN, Giménez J et al (2007) Study of the wavelength effect in the photolysis and heterogeneous photocatalysis. Catal Today 129:231–239
Beranek R, Neumann B, Sakthivel S et al (2007) Exploring the electronic structure of nitrogen-modified TiO2 photocatalysts through photocurrent and surface photovoltage studies. Chem Phys 339:11–19
Bhatkhande DS, Kamble SP, Sawant SB et al (2004) Photocatalytic and photochemical degradation of nitrobenzene using artificial ultraviolet light. Chem Eng J 102:283–290
Bouzaida I, Ferronato C, Chovelon JM et al (2004) Heterogeneous photocatalytic degradation of the anthraquinonic dye, Acid Blue 25 (AB25): a kinetic approach. J Photochem Photobiol A 168:23–30
Chun H, Yizhong W, Hongxiao T (2000) Destruction of phenol aqueous solution by photocatalysis or direct photolysis. Chemosphere 41:1205–1209
Clayden J, Warren S, Greeves N et al (2001) Organic chemistry. Oxford University Press, New York
Colombo DP Jr, Bowman RM (1996) Does interfacial charge transfer compete with charge carrier recombination? A femtosecond diffuse reflectance investigation of TiO2 nanoparticles. J Phys Chem 100:18445–18449
Colombo DP Jr, Skinner DE, Cavaleri JJ et al (1995a) Femtosecond spectroscopy of quantum- and bulk-sized semiconductor particles. Paper presented at the 210th ACS National Meeting, American Chemical Society. 20–24 August, Chicago, 1995
Colombo DP Jr, Roussel KA, Saeh J et al (1995b) Femtosecond study of the intensity dependence of electron-hole dynamics in TiO2 nanoclusters. Chem Phys Lett 232:207–214
Curcó D, Giménez J, Addardak A (2002) Effects of radiation absorption and catalyst concentration on the photocatalytic degradation of pollutants. Catal Today 76:177–188
Dinga H, Suna H, Shan Y (2005) Preparation and characterization of mesoporous SBA-15 supported dye-sensitized TiO2 photocatalyst. J Photochem Photobiol A 169:101–107
Dodd AC, McKinley AJ, Saunders M et al (2006) Effect of particle size on the photocatalytic activity of nanoparticulate zinc oxide. J Nanopart Res 8:43–51
Engel T, Reid P (2006) Physical chemistry. Pearson Education, San Fransisco
Evgenidou E, Fytianos K, Poulios I (2005) Semiconductor-sensitized photodegradation of dichlorvos in water using TiO2 and ZnO as catalysts. Appl Catal B 59:81–89
Fernández E, Figuera JM, Tobar A (1979) Use of potassium ferrioxalate actinometer below 254 nm. J Photochem 11:69–71
Friesen DA, Morello L, Headleya JV et al (2000) Factors influencing relative efficiency in photo-oxidations of organic molecules by Cs3PW12O40 and TiO2 colloidal photocatalysts. J Photochem Photobiol A 133:213–220
Fu X, Clark LA, Zeltner WA et al (1996) Effects of reaction temperature and water vapor content on the heterogeneous photocatalytic oxidation of ethylene. J Photochem Photobiol A 97:181–186
Gaya UI (2011) Comparative analysis of ZnO−catalyzed photo−oxidation of p−chlorophenols. Eur J Chem 2:163–167
Goldstein S, Rabani J (2008) The ferrioxalate and iodide–iodate actinometers in the UV region. J Photochem Photobiol A 193:50–55
Grätzel M, Frank AJ (1982) Interfacial electron-transfer reactions in colloldal semiconductor dispersions. Kinetic Analysis. J Phys Chem 86:2964–2967
Hatchard CG, Parker CA (1956) A newsensitive chemical actinometer. II. Potassium, ferric oxalate as a standard chemical actinometer. Proc R Soc London Ser A 235:518–536
Herrmann J-M (1999) Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants. Catal Today 53:115–129
Hoffmann MR, Martin ST, Choi W et al (1995) Environmental applications of semiconductor photocatalysis. Chem Rev 95:69–96
Huqul M, Ercaq E, Apak R (2002) Kinetic studies on UV-photodegradation of some chlorophenols using TiO2 catalyst. J Environ Sci A: Tox Hazard Subst Environ Eng 37(3):365–83
Jankowski JJ, Kieber DJ, Mopper K (1999) Nitrate and nitrite ultraviolet actinometers. Photochem Photobiol 70:319–328
Karunakaran C, Senthilvelan S (2005) Photooxidation of aniline on alumina with sunlight and artificial UV light. Catal Commun 6:159–165
Klabunde KJ, Richards RM (eds) (2009) Nanoscale materials in chemistry. Wiley, New Jersey
Kormann C, Bahnemann DW, Hoffman MR (1991) Photolysis of chloroform and other organic molecules in aqueous TiO2 suspensions. Environ Sci Technol 25:494–500
Kraeutler B, Bard AJ (1978) Heterogeneous photocatalytic decomposition of saturated carboxylic acids on TiO2 powder decarboxylative route to alkanes. J Am Chem Soc 100(19):5958
Kuhn HJ, Braslavsky SE, Schmidt R (2004) Chemical actinometry (IUPAC technical report). Organic and biomolecular chemistry division, subcommittee on photochemistry, International Union of Pure and Applied Chemistry. Pure Appl Chem 76:2105–2146
Kumar KV, Porkodi K, Selvaganapathi A (2007) Constrain in solving Langmuir-Hinshelwood kinetic expression for the photocatalytic degradation of Auramine O aqueous solutions by ZnO catalyst. Dyes Pigm 75:246–249
Lee J, Kim J, Choi W (2007) Ferrioxalate-polyoxometalate system as a new chemical actinometer. Environ Sci Technol 41:5433–5438
Leng WH, Zhang Z, Zhang JQ (2003) Photoelectrocatalytic degradation of aniline over rutile TiO2/Ti electrode thermally formed at 600 °C. J Mol Catal A: Chem 206:239–252
Li D, Haneda H (2003) Morphologies of zinc oxide particles and their effects on photocatalysis. Chemosphere 51:129–137
Li D, Haneda H, Ohashi N et al (2005) Morphological reform of ZnO particles induced by coupling with MOx (M = V, W, Ce) and the effects on photocatalytic activity. Thin Solid Films 486:20–23
McMurray TA, Dunlop PSM, Byrne JA (2006) The photocatalytic degradation of atrazine on nanoparticulate TiO2 films. J Photochem Photobiol A 182:43–51
Mehrotra K, Yablonsky GS, Ray AK (2003) Kinetic studies of photocatalytic degradation in a TiO2 Slurry System: Distinguishing working regimes and determining rate dependences. Ind Eng Chem Res 42:2273–2281
Minero C, Vione D (2006) A quantitative evaluation of the photocatalytic performance of TiO2 slurries. Appl Catal B 67:257–269
Montalti M, Credi A, Prodi L et al (2006) Handbook of Photochemistry 3rd edn. Taylor and Francis, USA
Mortimer RG (ed) (2008) Physical chemistry. Elsevier Academic Press, Canada
Muneer M, Theurich J, Bahnemann D (2001) Titanium dioxide mediated photocatalytic degradation of 1,2-diethyl phthalate. J Photochem Photobiol A 143:213–219
Muradov NZ, Raissi AT, Muzzey D et al (1996) Selective photocatalytic destruction of VOCs. Sol Energy 56(5):445–453
Puma GL, Yue PL (2002) Effect of the radiation wavelength on the rate of photocatalytic oxidation of organic pollutants. Ind Eng Chem Res 41:5594–5600
Qamar M, Muneer M, Bahnemann D (2006) Heterogeneous photocatalysed degradation of two selected pesticide derivatives, triclopyr and daminozide in aqueous suspensions of titanium dioxide. J Environ Manage 80:99–106
Rothenberger G, Moser J, Gratzel M et al (1985) Charge carrier trapping and recombination dynamics in small semiconductor particles. J Am Chem Soc 107:8054–8059
Salinaro A, Emeline AV, Zhao J et al (1999) Terminology, relative photonic efficiencies and quantum yields in heterogeneous photocatalysis. Part I: experimental determination of quantum yield. Pure Appl Chem 71:321–335
San N, Hatipoğlu A, Koçtürk G et al (2002) Photocatalytic degradation of 4-nitrophenol in aqueous TiO2 suspensions: theoretical prediction of the intermediates. J Photochem Photobiol A 146:189–197
Santos AR, Ballardini R, Belser P et al (2009) Photochemical investigation of a photochromic diarylethene compound that can be used as a wide range actinometer. Photochem Photobiol Sci 8:1734–1742
Saquib M, Muneer M (2003) TiO2-mediated photocatalytic degradation of a triphenyl methane dye (gentian violet), in aqueous suspensions. Dyes Pigm 56:37–49
Serpone N (1997) Relative photonic efficiencies and quantum yields in heterogeneous photocatalysis. J Photochem Photobiol A 104:1–12
Serpone N, Lawless D, Khairutdinov R et al (1995) Subnanosecond relaxation dynamics in TiO2 colloidal sols (Particle sizes R, = 1.0- 13.4 nm). Relevance to heterogeneous photocatalysis. J Phys Chem 99:16655–16661
Serpone N, Salinaro A (1999) Terminology, relative photonic efficiencies and quantum yields in heterogeneous photocatalysis. Part I: suggested protocol (Technical Report). Pure Appl Chem 71:303–320
Serpone N, Sauve G, Koch R et al (1996) Standardization protocol of process efficiencies and activation parameters in heterogeneous photocatalysis: relative photonic efficiencies ζr. J Photochem Photobiol A 94:191–203
Silva CG, Wang W, Faria JL (2006) Photocatalytic and photochemical degradation of mono-, di- and tri-azo dyes in aqueous solution under UV irradiation. J Photochem Photobiol A 181:314–324
Soares ET, Lansarin MA, Moro CC (2001) A study of process variables for the photocatalytic degradation of Rhodamine B. Braz J Chem Eng 24(01):29–36
Stylidi M, Kondarides DI, Verykios XE (2004) Visible light-induced photocatalytic degradation of Acid Orange 7 in aqueous TiO2 suspensions. Appl Catal B 47:189–201
Tahiri H, Serpone N, Le vanMR (1996) Application of concept of relative photonic efficiencies and characterization of a new titania photocatalyst designed for environmental remediation. J Photochem Photobiol A 93:199–203
Tariq MA, Faisal M, Muneer M et al (2007) Photochemical reactions of a few selected pesticide derivatives and other priority organic pollutants in aqueous suspensions of titanium dioxide. J Mol Catal A: Chem 265:231–236
Theurich J, Lindner M, Bahnemann DW (1996) Photocatalytic degradation of 4-chlorophenol in aerated aqueous titanium dioxide suspensions: a kinetic and mechanistic study. Langmuir 12:6368–6376
Tunesi S, Anderson MA (1978) Photocatalysis of 3,4-DCB in TiO2 aqueous suspension; Effects of temperature and light intensity; CIR-FTIR interfacial analysis. Chemosphere 16(7):1447–1456
Vinodgopal K, Bedja I, Kamat PV (1996) Nanostructured semiconductor films for photocatalysis. Photoelectrochemical behavior of SnO2/TiO2 composite systems and its role in photocatalytic degradation of a textile azo dye. Chem Mater 8:2180–2187
Vorontsov AV, Stoyanova IV, Kozlov DV et al (2000) Kinetics of the photocatalytic oxidation of gaseous acetone over platinized titanium dioxide. J Catal 189:360–369
Wang C-M, Heller A, Gerischer H (1992) Palladium catalysis of O2 reduction by electrons accumulated on TiO2 particles during photo-assisted oxidation of organic compounds. J Am Chem Soc 114:5230–5234
Wang XH, Li JG, Kamiyama H et al (2006) Wavelength-Sensitive Photocatalytic degradation of methyl orange in aqueous suspension over Iron(III)-doped TiO2 Nanopowders under UV and visible light irradiation. J Phys Chem B 110:6804–6809
Wilke K, Breuer HD (1999) The influence of transition metal doping on the physical and photocatalytic properties of titania. J Photochem Photobiol A 121:49–53
Wright MR (2006) An Introduction to chemical kinetics. Wiley, England
Yang L, Liu Z (2007) Study on light intensity in the process of photocatalytic degradation of indoor gaseous formaldehyde for saving energy. Energ Convers Manage 48:882–889
Yang L, Yu LE, Ray MB (2009) Photocatalytic oxidation of paracetamol: dominant reactants, intermediates, and reaction mechanisms. Environ Sci Technol 43:460–465
Yang X, Tamai N (2001) How fast is interfacial hole transfer? In situ monitoring of carrier dynamics in anatase TiO2 nanoparticles by femtosecond laser spectroscopy. Phys Chem Chem Phys 3:3393–3398
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2014 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Gaya, U. (2014). Kinetic Concepts of Heterogeneous Photocatalysis. In: Heterogeneous Photocatalysis Using Inorganic Semiconductor Solids. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-7775-0_2
Download citation
DOI: https://doi.org/10.1007/978-94-007-7775-0_2
Published:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-007-7774-3
Online ISBN: 978-94-007-7775-0
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)