Issue 43, 2020

Morphology of Cu clusters supported on reconstructed polar ZnO (0001) and (000[1 with combining macron]) surfaces

Abstract

Unbiased Monte Carlo procedures are applied to investigate the structure of Cu clusters of various sizes deposited over reconstructed polar ZnO surfaces. Four distinct reconstructed polar ZnO surfaces (two Zn terminated (0001) reconstructions and two O terminated (000[1 with combining macron]) reconstructions) were investigated, having previously been determined to be the most stable under typical conditions, as revealed by the grand canonical ensemble studies. Random sampling was performed considering ∼400 000 random initial structural configurations of Cu atoms over the ZnO surfaces, with each structure being optimised using interatomic potential techniques, and the most stable resultant structures being refined using a plane-wave DFT approach. The investigation reveals the key role of surface adatoms and vacancies arising from the reconstruction of the polar ZnO surface in determining the morphology of deposited Cu clusters. Strong Cu–Zn interactions play an essential role in Cu cluster growth, with reconstructed polar ZnO surfaces featuring sites with undercoordinated Zn surface atoms promoting highly localised three dimensional Cu cluster morphologies, whist reconstructions featuring undercoordinated O atoms tend to result in more planar Cu clusters, in order to maximise the favourable Cu–Zn interaction. This is the first study that evaluates the thermodynamically most stable Cu/ZnO structures using realistic reconstructed ZnO polar surfaces, and thus provides valuable insights into the factors affecting Cu cluster growth over ZnO surfaces, as well as model catalyst surfaces that can be utilised in future computational studies to explore catalytic activity for key processes such as CO2 and CO hydrogenation to methanol.

Graphical abstract: Morphology of Cu clusters supported on reconstructed polar ZnO (0001) and (000 [[1 with combining macron]] ) surfaces

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2020
Accepted
13 Oct 2020
First published
13 Oct 2020
This article is Open Access
Creative Commons BY license

J. Mater. Chem. A, 2020,8, 22840-22857

Morphology of Cu clusters supported on reconstructed polar ZnO (0001) and (000[1 with combining macron]) surfaces

M. D. Higham, D. Mora-Fonz, A. A. Sokol, S. M. Woodley and C. R. A. Catlow, J. Mater. Chem. A, 2020, 8, 22840 DOI: 10.1039/D0TA08351H

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