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Cooperative Interactions between Surface Terminations Explain Photocatalytic Water Splitting Activity on SrTiO3

Vidushi Sharma1,2,3,4,*, Benjamin Bein3, Amanda Lai3, Betül Pamuk5, Cyrus E. Dreyer3,6, Marivi Fernández-Serra3,4,†, and Matthew Dawber3,‡

  • 1Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
  • 2Center for Nonlinear Studies (CNLS), Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
  • 3Department of Physics and Astronomy, Stony Brook University, Stony Brook, New York 11794-3800, USA
  • 4Institute for Advanced Computational Science, Stony Brook University, Stony Brook, New York 11794-3800, USA
  • 5School of Applied and Engineering Physics, Cornell University, Ithaca, New York 14853, USA
  • 6Center for Computational Quantum Physics, Flatiron Institute, 162 5th Avenue, New York, New York 10010, USA

  • *vidushi@lanl.gov
  • †maria.fernandez-serra@stonybrook.edu
  • ‡matthew.dawber@stonybrook.edu
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PRX Energy 1, 023002 – Published 14 July, 2022

DOI: https://doi.org/10.1103/PRXEnergy.1.023002

Abstract

SrTiO3 is a highly efficient photocatalyst for the overall water splitting reaction under UV irradiation. However, an atomic-level understanding of the active surface sites responsible for the oxidation and reduction reactions is still lacking. Here we present a unified experimental and computational account of the photocatalytic activity at the SrO and TiO2 terminations of aqueous solvated [001] SrTiO3. Our experimental findings show that the overall water-splitting reaction proceeds on the SrTiO3 surface only when the two terminations are simultaneously exposed to water. Our simulations explain this, showing that the photogenerated hole-driven oxidation primarily occurs at SrO surfaces in a sequence of four single hole transfer reactions, while the TiO2 termination effects the crucial band alignment of the photocatalyst relative to the water oxidation potential. The present work elucidates the interdependence of the two chemical terminations of SrTiO3 surfaces, and has consequent implications for maximizing sustainable solar-driven water splitting.

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synopsis

The Brains and Brawn Behind Splitting Water

Published 14 July, 2022

Researchers reveal how different facets of a photocatalyst’s surface cooperate to extract hydrogen from water.

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Reducing our dependence on fossil fuels is one of the key challenges of this century. For decades, photocatalytic water splitting has been touted as a promising avenue for producing sustainable alternative fuel from abundant sunlight; however, development in this area has been slow. One factor in the slow progress is the difficulty of characterizing and modeling heterogeneous catalysis, since it requires atomistic knowledge of the local surface morphology and electronic structure during the chemical reaction. In this work, the authors combine experimental observations from scanning probe techniques with first-principles computations, based on density-functional theory (DFT) and molecular dynamics (MD) simulations, to obtain such an atomistic picture of photocatalytic water splitting on the surface of SrTiO3. Though this material's band gap is too large to allow high-efficiency solar photocatalysis, SrTiO3 is often used as a model system for understanding the process and developing design principles to be applied to other systems. However, even in this “model” system, some of the basic aspects of the water-splitting reaction were not known.

This work demonstrates that a specific surface structure with a mixture of different atomic surface terminations is required for efficient water splitting. This is a surprising and unexpected result; indeed, it was assumed that a single atomic termination (i.e., either SrO or TiO2) fulfilled all of the requirements for catalyzing the water-splitting reaction. However, atomic-force microscopy characterization before and after water-splitting reactions on samples with carefully controlled surface termination clearly shows the necessity for mixed terminations. Using DFT calculations and MD simulations, the authors determine the atomistic model of the reaction, clearly identifying the separate roles that the different surface terminations and catalytic active sites play in the overall efficiency of the reaction.

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PRX Energy 1, 023002– Published 14 July, 2022
  • Received 10 February 2022
  • Revised 23 May 2022
  • Accepted 3 June 2022
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