Simon Gelin^1*, Nicole E. Kirchner-Hall^1,2, Rowan R. Katzbaer³, Monica J. Theibault⁴, Yihuang Xiong¹, Wayne Zhao^1,5, Mohammed M. Khan^1,6, Eric Andrewlavage¹, Paul Orbe¹, Steven M. Baksa¹, Matteo Cococcioni⁷, Iurii Timrov⁸, Quinn Campbell⁹, Héctor Abruña⁴, Raymond E. Schaak¹⁰, Ismaila Dabo^1*

1 Department of Materials Science and Engineering, and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA

2 Science & Technology, Corning Incorporated, Corning, New York, USA

3 Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA

4 Department of Chemistry and Chemical Biology, Cornell University, 245 Feeney Way, Ithaca, New York 14850, United States

5 Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, California 94720, USA

6 Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900, Kingdom of Saudi Arabia

7 Department of Physics, University of Pavia, via Bassi 6, Pavia I-27100, Italy

8 Theory and Simulation of Materials (THEOS), and National Centre for Computational Design and Discovery of Novel Materials (MARVEL)

9 Center for Computing Research, Sandia National Laboratories, Albuquerque, NM, USA

10 Department of Chemistry, Department of Chemical Engineering, and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA

* Corresponding authors emails: gelin@psu.edu, dabo@psu.edu

DOI10.24435/materialscloud:zh-14 [version v1]

Publication date: Oct 23, 2023

How to cite this record

Simon Gelin, Nicole E. Kirchner-Hall, Rowan R. Katzbaer, Monica J. Theibault, Yihuang Xiong, Wayne Zhao, Mohammed M. Khan, Eric Andrewlavage, Paul Orbe, Steven M. Baksa, Matteo Cococcioni, Iurii Timrov, Quinn Campbell, Héctor Abruña, Raymond E. Schaak, Ismaila Dabo, Ternary oxides of s- and p-block metals for photocatalytic solar-to-hydrogen conversion, Materials Cloud Archive 2023.161 (2023), https://doi.org/10.24435/materialscloud:zh-14

Description

Oxides containing metals or semimetals from the p-block of the periodic table, e.g., indium oxide or antimony oxide, are of interest as transparent conductors and light absorbers for solar energy conversion due to the tunability of their electronic conductivity and optical absorption. Comparatively, these oxides have found limited applications in solar-to-hydrogen photocatalysis primarily due to their high electronegativity, which impedes electron transfer for converting protons into hydrogen. We have shown recently that inserting s-block metal cations into p-block oxides is effective at lowering electronegativities while affording further control of band gaps. Here, we explain the origins of this dual tunability by demonstrating the mediator role of s-block metal cations in modulating orbital hybridization while not contributing to frontier electronic states. From this result, we carry out a comprehensive computational study of 109 ternary oxides of s- and p-block metal elements as candidate photocatalysts for solar hydrogen generation. We downselect the most desirable materials using band gaps and band edges obtained from Hubbard-corrected density-functional theory with Hubbard parameters computed entirely from first principles, evaluate the stability of these oxides in aqueous conditions, and characterize experimentally four of the remaining materials, synthesized with high phase uniformity, to critically assess the accuracy of the computational models. We thus propose nine oxide semiconductors, including CsIn₃O₅, Sr₂In₂O₅, and KSbO₂ which, to the extent of our literature review, have not been previously considered as water-splitting photocatalysts. This record contains the data for the simulations discussed in our manuscript.

Materials Cloud sections using this data

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File name	Size	Description
archive.tar.gz MD5md5:90999ad3e047e63342c90f51b5d9638f	166.6 KiB	This record contains the data for the simulations discussed in our manuscript: DFT, DFT+U, HSE06, and slab calculations.

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Keywords

Photocatalysis DFT+U MARVEL