Issue 8, 2021

Theoretical prediction by DFT and experimental observation of heterocation-doping effects on hydrogen adsorption and migration over the CeO2(111) surface

Abstract

Hydrogen (H) atom adsorption and migration over the CeO2-based materials surface are of great importance because of its wide applications to catalytic reactions and electrochemical devices. Therefore, comprehensive knowledge for controlling the H atom adsorption and migration over CeO2-based materials is crucially important. For controlling H atom adsorption and migration, we investigated irreducible divalent, trivalent, and quadrivalent heterocation-doping effects on H atom adsorption and migration over the CeO2(111) surface using density functional theory (DFT) calculations. Results revealed that the electron-deficient lattice oxygen (Olat) and the flexible CeO2 matrix played key roles in strong adsorption of H atoms. Heterocations with smaller valence and smaller ionic radius induced the electron-deficient Olat. In addition, smaller cation doping enhanced the CeO2 matrix flexibility. Moreover, we confirmed the influence of H atom adsorption controlled by doping on surface proton migration (i.e. surface protonics) and catalytic reaction involving surface protonics (NH3 synthesis in an electric field). Results confirmed clear correlation between H atom adsorption energy and surface protonics.

Graphical abstract: Theoretical prediction by DFT and experimental observation of heterocation-doping effects on hydrogen adsorption and migration over the CeO2(111) surface

Supplementary files

Article information

Article type
Paper
Submitted
04 Nov 2020
Accepted
17 Jan 2021
First published
26 Jan 2021
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2021,23, 4509-4516

Theoretical prediction by DFT and experimental observation of heterocation-doping effects on hydrogen adsorption and migration over the CeO2(111) surface

K. Murakami, Y. Mizutani, H. Sampei, A. Ishikawa, Y. Tanaka, S. Hayashi, S. Doi, T. Higo, H. Tsuneki, H. Nakai and Y. Sekine, Phys. Chem. Chem. Phys., 2021, 23, 4509 DOI: 10.1039/D0CP05752E

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