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Visible light photolysis of hydrogen iodide using sensitized layered metal oxide semiconductors: The role of surface chemical modification in controlling back electron transfer reactions
The internally platinized wide bandgap semiconductor K4Nb6O17 can be sensitized by [(bpy)2Ru(4-(2,2a??-bipyrid-4-yl)-phenylphosphonic acid](PF6)2 (1). In aqueous iodide solutions at pH 2, the visible light photolysis of HI, to form H2 and I3-, is catalyzed by 1/K4-xHxNb6O17/Pt. The strong bond between the surface and the phosphonate group of 1 allows one to adsorb other surface species, which decrease the rate of the back electron transfer reaction between conduction band electrons and I3- ions. Methylphosphonic acid and undecylphosphonic acid do not form good surface monolayers on 1/K4-xHxNb6O17 and do not increase the rate of hydrogen evolution. Anionic surface modifiers [TiNbO5]nn-, derived from exfoliation of KTiNbO5, and poly(styrenesulfonate), PSS, increase the initial hydrogen evolution rate by factors of 3 and 5, respectively. In the latter case, the initial quantum yield for HI photolysis is ca. 3%. Transient diffuse reflectance spectroscopy was used to monitor the formation and disappearance of I3- ions with 1/K4-xHxNb6O17 and PSS/ 1/K4-xHxNb6O17. The rate constant for the back electron transfer reaction between conduction band electrons and I3- ions decreases from 3.17 (A¡À0.03) A? 107 to 3.01(A¡À0.02) A? 106 M-1 s-1 upon adsorption of PSS.
Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Application In Synthesis of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II). In my other articles, you can also check out more blogs about 15746-57-3
Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI