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Photofunctional construct that interfaces molecular cobalt-based catalysts for H production to a visible-light-absorbing semiconductor

Journal of the American Chemical Society, ISSN: 0002-7863, Vol: 135, Issue: 32, Page: 11861-11868
2013
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Article Description

Molecular cobalt-containing hydrogen production catalysts are grafted to a visible-light-absorbing semiconductor. The attachment procedure exploits the UV-induced immobilization chemistry of vinylpyridine to p-type (100) gallium phosphide (GaP). Single step surface-initiated photopolymerization yields a covalently attached polymer with pendent pyridyl groups that provide attachment points for assembling cobaloxime catalysts. Successful attachment is characterized by grazing angle attenuated total reflection Fourier transform infrared spectroscopy (GATR-FTIR), which shows distinct vibrational modes associated with the catalyst, as well as X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure spectroscopy (XANES) that confirm the presence of intact Co complex on the surface. The Co-functionalized photocathode shows significantly enhanced photoelectrochemical (PEC) performance in aqueous conditions at neutral pH, compared to results obtained on GaP without attached cobalt complex. PEC measurements, at 100 mW cm illumination, yield a 2.4 mA cm current density at a 310 mV underpotential. © 2013 American Chemical Society.

Bibliographic Details

Krawicz, Alexandra; Yang, Jinhui; Anzenberg, Eitan; Yano, Junko; Sharp, Ian D; Moore, Gary F

American Chemical Society (ACS)

Chemical Engineering; Chemistry; Biochemistry, Genetics and Molecular Biology

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