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Photoelectrochemistry of metalloporphyrin-modified GaP semiconductors

Abstract

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.

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Acknowledgements

This work was supported by the National Science Foundation under Early Career Award 1653982 (polymeric surface chemistry) and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Early Career Award DE-SC0021186 (analysis of recombination kinetics). G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. B.L.W. was supported by an IGERT-SUN fellowship funded by the National Science Foundation (1144616) and the Phoenix Chapter of the ARCS Foundation. D.N. was supported by the Heiwa Nakajima Foundation. XPS data were collected at the Eyring Materials Center at Arizona State University. NMR studies were performed using the Magnetic Resonance Research Center at Arizona State University.

Funding

This work was supported by the National Science Foundation under Early Career Award 1653982 (polymeric surface chemistry) and by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Early Career Award DE-SC0021186 (analysis of recombination kinetics). G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. B.L.W. was supported by an IGERT-SUN fellowship funded by the National Science Foundation (1144616) and the Phoenix Chapter of the ARCS Foundation. D.N. was supported by the Heiwa Nakajima Foundation.

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Correspondence to Gary F. Moore.

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Nishiori, D., Wadsworth, B.L., Reyes Cruz, E.A. et al. Photoelectrochemistry of metalloporphyrin-modified GaP semiconductors. Photosynth Res 151, 1–10 (2022). https://doi.org/10.1007/s11120-021-00834-2

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  • DOI: https://doi.org/10.1007/s11120-021-00834-2

Keywords

  • Artificial photosynthesis
  • Photoelectrochemistry
  • Molecular-modified photocathodes
  • Metalloporphyrins
  • Gallium phosphide
  • Hydrogen evolution