Effects of Metal Ions on H2 Generation during Photolysis of Suspended TiO2 in Aqueous Systems
DOI:
https://doi.org/10.6000/1929-5030.2015.04.01.5Keywords:
H2, TiO2, hole scavenger, photolysis, metal ions, nanoparticles.Abstract
Nowadays, photocatalysis is being applied as a promising technique for decontamination, purification, deodorization, etc. of polluted air and wastewaters. This technique attempts also to generate renewable and non-polluting fuels utilizing various carbon and hydrogen sources. In this context, studies on photo-catalytic generation of H2 using 0.1% w/v TiO2 photo catalyst as a suspension in water was carried out using 350 nm light. This was explored further in presence of various metal ions such as Ag+, Cu2+, Fe2+, Au3+ and V5+ at different ambient such as air and CO2, in presence of a hole scavenger (2-propanol and formic acid). H2 yields in CO2-purged systems as analyzed in GC-TCD were reasonably higher, and increased further when metal ions were added into the systems. Based on H2 yields, HCOOH was found to be a more supportive hole scavenger as compared to 2-propanol in metal ions containing systems. Besides the formation of low to high concentrations of various gaseous products, nanoparticles of gold, silver and copper were also observed as photolysis products. This indicated that the presence of both reduced metal ions and their in-situ generated nanoparticles at various stages either in the free/unbound and/or associated with TiO2 photocatalyst in aqueous systems, together play a significant role in enhancing the H2 yields.References
[1] Fujishima A, Rao TN, Tryk DA. Titanium dioxide photocatalysis. J Photochem Photobiol C:Photochem Rev 2000; 1: 1-21. http://dx.doi.org/10.1016/S1389-5567(00)00002-2
[2] Fujishima A, Kohayakawa K, Hona K. Hydrogen production under sunlight with an electrochemical photocell. J Electrochem Soc 1975; 122: 1487-9. http://dx.doi.org/10.1149/1.2134048
[3] Kawai T, Sakata T. Photocatalytic hydrogen production from liquid methanol and water. J Chem Soc Chem Communicat 1980; 694-5. http://dx.doi.org/10.1039/C39800000694
[4] Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972; 238: 37-8. http://dx.doi.org/10.1038/238037a0
[5] Hoffmann MR, Martin ST, Choi W, Bahnemann DW. Environmental applications of semiconductor photocatalysis. Chem Rev 1995; 95: 69-96. http://dx.doi.org/10.1021/cr00033a004
[6] Bahnemann DW. in Photochemical conversion and storage of solar energy, eds. Pelizzetti E and Schiavello M, Kluwer Academic Publishers, Dordrecht, 1991; 251. http://dx.doi.org/10.1007/978-94-011-3396-8_15
[7] Dey GR, Kishore K. Carbon dioxide reduction: A brief review. in Photo/Electrochemistry & Photobiology in the Environment, Energy and Fuel (PE&PB in EEF), Kaneco S (Ed.), Research Signpost, Kerala, India, 2005; 357. http://dx.doi.org/10.1016/S1003-9953(07)60052-8
[8] Dey GR. Chemical reduction of CO2 to different products during photo-catalytic reaction on TiO2 under diverse conditions: An overview. J Natural Gas Chem 2007; 16: 217- 26. http://dx.doi.org/10.1016/S1003-9953(07)60052-8
[9] Rabani J, Metheson MS. Pulse radiolytic determination of pK for hydroxyl ionic dissociation in water. J Am Chem Soc 1964; 86: 3175-6. http://dx.doi.org/10.1021/ja01069a058
[10] Bieski BHJ, Cabelli DE, Arudi RL, Ross AB. Reactivity of HO2/O2 - radicals in aqueous solution. J Phys Chem Ref Data 1985; 14: 1041-100. http://dx.doi.org/10.1063/1.555739
[11] Anpo M. Photocatalysis on small particle TiO2 catalysts. Reaction intermediates and reaction mechanism. Res Chem Intermed 1989; 11: 67-106. http://dx.doi.org/10.1007/BF03051818
[12] Jaeger CD, Bard AJ. Spin trapping and electron spin resonance detection of radical intermediates in the photodecomposition of water at TiO2 particulate systems. J Phys Chem 1979; 83: 3146-52. http://dx.doi.org/10.1021/j100487a017
[13] Dey GR, Belapurkar AD, Kishore K. Photoreduction of carbon dioxide to methane using TiO2 as suspension in water. J Photochem Photobiol A: Chem 2004; 163: 501-6. http://dx.doi.org/10.1016/j.jphotochem.2004.01.022
[14] Dey GR, Pushpa KK. Carbon dioxide and methane generated during photo-catalytic redox reaction of alcohols on TiO2 suspension in aqueous solutions. Res Chem Intermed 2006; 32: 725-36. http://dx.doi.org/10.1163/156856706778606462
[15] Dey GR, Pushpa KK. Generation of different products on photocatalytic reaction on TiO2 suspension in aqueous solutions with and without a hole scavenger at diverse ambient conditions. Res Chem Intermed 2007; 33: 631-44. http://dx.doi.org/10.1163/156856707781749883
[16] Dey GR, Nair KNR, Pushpa KK. Photolysis studies on HCOOH and HCOO- in presence of TiO2 photo catalyst as suspension in aqueous medium. J Natural Gas Chem 2009; 18:50-4. http://dx.doi.org/10.1016/S1003-9953(08)60075-4
[17] Langford JI, Wilson AJC. Scherrer after sixty years: A survey and some new results in the determination of crystallite size. J Appl Crystal 1978; 11: 102-13. http://dx.doi.org/10.1107/S0021889878012844
[18] Anderson JR. Structure of Metallic Catalysts, Academic Press Inc., London, 1975; 365.
[19] Dey GR, Remita H, Mostafavi M. Radiolytic reduction of Fe(II) in 2-propanol. Chem Phys Lett 2006; 431: 83-7. http://dx.doi.org/10.1016/j.cplett.2006.09.055
[20] William Jr. RK, Clifford SG. Kinetics of the oxidation of vanadium (II) and Vanadium (III) ions by perchlorate ions. J Phys Chem 1954; 58: 29-33. http://dx.doi.org/10.1021/j150511a007
[21] Joint Committee on Powder Diffraction Standards, Card No. 21-1272 and 4-784
[22] Belapurkar AD, Kamble VS, Dey GR. Photo-oxidation of ethylene in gas phase and methanol and formic acid in liquid phase on synthesized TiO2 and Au/TiO2 catalysts. Mater Chem Phys 2010; 123: 801-5. http://dx.doi.org/10.1016/j.matchemphys.2010.05.063
[23] Christy AJ, Umadevi M. Synthesis and characterization of monodispersed silver nanoparticles. Adv Natural Sci: Nanosci Nanotechnol 2012; 3: 035013(1-4). http://dx.doi.org/10.1088/2043-6262/3/3/035013
[24] Mostafavi M, Marignier JL, Amblard J, Belloni J. Nucleation dynamics of silver aggregates simulation of photographic development processes. Radiat Phys Chem 1989; 34: 605- 17. http://dx.doi.org/10.1016/1359-0197(89)90069-6
[25] Dey GR, El Omar AK, Jacob JA, Mostafavi M, Belloni J. Mechanism of trivalent gold reduction and reactivity of transient divalent and monovalent gold ions studied by gamma- and pulse radiolysis. J Phys Chem A 2011; 115: 383-91. http://dx.doi.org/10.1021/jp1096597
[26] Dey GR. Reduction of copper ion to metal copper in alcohol: A radiation chemical study. Radiat Phys Chem 2005; 74: 172-84. http://dx.doi.org/10.1016/j.radphyschem.2005.04.012
[27] Schwarz HA, Dodson RW. Reduction potentials of CO2 - and alcohol radicals. J Phys Chem 1989; 93: 409-14. http://dx.doi.org/10.1021/j100338a079
[28] Hirano K, Asayama H, Hoshino A, Wakatsuki H. Metal powder addition effect on photocatalytic reactions and photogenerated electric charge collected at an inert electrode in aqueous TiO2 suspensions. J Photochem Photobiol A Chem 1997; 110: 307-11. http://dx.doi.org/10.1016/S1010-6030(97)00201-3
[29] Mizuno T, Adhachi K, Ohta K, Saji A. Effects of CO2 pressure on photocatalytic reduction of CO2 using TiO2 solutions. J Photochem Photobiol A Chem 1996; 98: 87-90. http://dx.doi.org/10.1016/1010-6030(96)04334-1
[30] Mills A, Le Hunte S. An overview of semiconductor photocatalysis. J Photochem Photobiol A: Chem 1997; 108: 1-35. http://dx.doi.org/10.1016/S1010-6030(97)00118-4
[31] Dey GR. Significant roles of oxygen and unbound • OH radical in phenol formation during photo-catalytic degradation of benzene on TiO2 suspension in aqueous system. Res Chem Intermed 2009; 35: 573-87. http://dx.doi.org/10.1007/s11164-009-0066-0
[32] Buxton GV, Greenstock CL, Helman WP, Ross AB. Critical review of rate constants for reactions of hydrated electron, hydrogen atoms and hydroxyl radicals (OH/O- ) in aqueous solution. J Phys Chem Ref Data 1988; 17: 513-886. http://dx.doi.org/10.1063/1.555805
[33] Choi W, Hoffmann MR. Novel photocatalytic mechanisms for CHCl3, CHBr3, and CCl3CO2 - degradation and the fate of photogenerated trihalomethyl radicals on TiO2. Environ Sci Technol 1997; 31: 89-94. http://dx.doi.org/10.1021/es960157k
[34] Kaneco S, Shimizu Y, Ohta K, Mizuno T. Photocatalytic reduction of high pressure carbon dioxide using TiO2 powders with a positive hole scavenger. J Photochem Photobiol A Chem 1998; 115: 223-6. http://dx.doi.org/10.1016/S1010-6030(98)00274-3
[35] Belloni J. Nucleation, growth and properties of nanoclusters studied by radiation chemistry: Application to catalysis. Catal Today 2006; 113: 141-56. http://dx.doi.org/10.1016/j.cattod.2005.11.082
[36] Subramanian V, Wolf EE, Kamat PV. Catalysis with TiO2/gold nanocomposites. Effect of metal particle size on the fermi level equilibration. J Am Chem Soc 2004; 126: 4943-50. http://dx.doi.org/10.1021/ja0315199
[37] Kamat PV. Photoinduced transformations in semiconductor– metal nanocomposite assemblies. Pure Appl Chem 2002; 74: 1693-706. http://dx.doi.org/10.1351/pac200274091693
[38] Belloni J. Metal nanocolloids. Curr Opinion Coll Interf 1996; 1: 184-96. http://dx.doi.org/10.1016/S1359-0294(96)80003-3
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2015-02-25
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Dey, G. (2015). Effects of Metal Ions on H2 Generation during Photolysis of Suspended TiO2 in Aqueous Systems. Journal of Applied Solution Chemistry and Modeling, 4(1), 63–71. https://doi.org/10.6000/1929-5030.2015.04.01.5
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