Photofunctional Construct That Interfaces Molecular Cobalt-Based Catalysts for H2 Production to a Visible-Light-Absorbing Semiconductor

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 CoIII 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.