Photoelectrochemistry of metalloporphyrin-modified GaP semiconductors

Photoelectrosynthetic materials provide a bioinspired approach for using the power of the sun to produce fuels and other value-added chemical products. However, there remains an incomplete understanding of the operating principles governing their performance and thereby effective methods for their assembly. Herein we report the application of metalloporphyrins, several of which are known to catalyze the hydrogen evolution reaction, in forming surface coatings to assemble hybrid photoelectrosynthetic materials featuring an underlying gallium phosphide (GaP) semiconductor as a light capture and conversion component. The metalloporphyrin reagents used in this work contain a 4-vinylphenyl surface-attachment group at the β-position of the porphyrin ring and a first-row transition metal ion (Fe, Co, Ni, Cu, or Zn) coordinated at the core of the macrocycle. In addition to describing the synthesis, optical, and electrochemical properties of the homogeneous porphyrin complexes, we also report on the photoelectrochemistry of the heterogeneous metalloporphyrin-modified GaP semiconductor electrodes. These hybrid, heterogeneous-homogeneous electrodes are prepared via UV-induced grafting of the homogeneous metalloporphyrin reagents onto the heterogeneous gallium phosphide surfaces. Three-electrode voltammetry measurements performed under controlled lighting conditions enable determination of the open-circuit photovoltages, fill factors, and overall current–voltage responses associated with these composite materials, setting the stage for better understanding charge-transfer and carrier-recombination kinetics at semiconductor|catalyst|liquid interfaces.