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Updated: May 9, 2026

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
Published on: October 5, 2019
Photofunctional construct that interfaces molecular cobalt-based catalysts for H2 production to a
Alexandra Krawicz1, Jinhui Yang, Eitan Anzenberg
1Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
Abstract:
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(III) 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(-2) illumination, yield a 2.4 mA cm(-2) current density at a 310 mV underpotential.
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