Calculations of the effect of catalyst size and structure on the electrocatalytic reduction of CO2 on Cu nanoclusters

Geoffrey R Weal; Kristinn Ingi Guðmundsson; Frank D Mackenzie; John R Whiting; Nicholas B Smith; Egill Skúlason; Anna L Garden

doi:10.1039/d3nr04956f

Calculations of the effect of catalyst size and structure on the electrocatalytic reduction of CO₂ on Cu nanoclusters

Nanoscale. 2024 Mar 7;16(10):5242-5256. doi: 10.1039/d3nr04956f.

Authors

Geoffrey R Weal^{1

2}, Kristinn Ingi Guðmundsson³, Frank D Mackenzie^{1

2}, John R Whiting^{1

2}, Nicholas B Smith^{1

2}, Egill Skúlason³, Anna L Garden^{1

2}

Affiliations

¹ Department of Chemistry, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand. anna.garden@otago.ac.nz.
² The MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, P.O. Box 600, Wellington 6140, New Zealand.
³ Science Institute and Faculty of Industrial Engineering, Mechanical Engineering and Computer Science, University of Iceland, VR-III, 107 Reykjavík, Iceland.

PMID: 38362911
DOI: 10.1039/d3nr04956f

Abstract

The structure and catalytic properties of Cu nanoclusters of sizes between 55 and 147 atoms were examined to understand if small Cu clusters could provide enhancement over traditional catalysts for the electrocatalysis of CO₂ to CO and carbon-based fuels, such as CH₄ and CH₃OH, compared to bulk Cu surfaces and large Cu nanoparticles. Clusters studied included Cu₅₅, Cu₇₈, Cu₁₀₁, Cu₁₂₄, and Cu₁₄₇, the structures of which were determined using global optimisation. The majority of Cu clusters examined were icosahedral, including the perfect closed-shell, partial-shell, elongated and distorted icosahedral clusters. Free energy diagrams for the reduction of CO₂ showed the potential required for the formation of CO is notably smaller for all cluster sizes considered, relative to Cu(111). Less variation is observed for the limiting potential for the formation of CH₄ and CH₃OH. However, it was found that clusters that are either a distorted motif or contain vacancy defects yielded the best activity and provide an interesting synthesis target for future experiments.