Light absorbing nanoparticles such as titanium dioxide, tungsten oxide, and hematite have been employed as supports for heterogenizing transition-metal-substituted polyoxometalate (POM) water oxidation catalysis (WOCs). These POM-based WOCs are known to be fast, selective, and oxidatively stable in their homogeneous phase. In heterogenized systems, such as on an electrode or other modified surfaces, distinguishing the durability and activity of the surface-bound POM versus leeched homogeneous POM is challenging. In this study, [Ru4(OH)2(H2O)2(a-XW9O34)2]10-, where X=Si4+, and P5+, have been immobilized on modified TiO2, WO3, and a-Fe2O3 nanoparticles and found to retain catalytic water oxidation activity after multiple use cycles under conditions similar to the homogenous POM-catalyzed light-induced water oxidation system (photosensitizer and sacrificial oxidant). Replacing the photosensitizer with a light-absorbing nanoparticle support may provide a more direct and stable heterogenized system for catalytic water oxidation. The interaction between POM and nanoparticle surface before and after catalysis has been studied using spectroscopic and microscopic methods.

Spectroscopic study of polyoxometalates immobilized on light-absorbing nanoparticles for robust light-induced water oxidation

248th National Meeting (2014)

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