The nature of active sites for carbon dioxide electroreduction over oxide-derived copper catalysts

Abstract

The active sites for CO2 electroreduction (CO2R) to multi-carbon (C2+) products over oxide-derived copper (OD-Cu) catalysts are under long-term intense debate. This paper describes the atomic structure motifs for product-specific active sites on OD-Cu catalysts in CO2R. Herein, we describe realistic OD-Cu surface models by simulating the oxide-derived process via the molecular dynamic simulation with neural network (NN) potential. After the analysis of over 150 surface sites through NN potential based high-throughput testing, coupled with density functional theory calculations, three square-like sites for C–C coupling are identified. Among them, Σ3 grain boundary like planar-square sites and convex-square sites are responsible for ethylene production while step-square sites, i.e. n(111) × (100), favor alcohols generation, due to the geometric effect for stabilizing acetaldehyde intermediates and destabilizing Cu–O interactions, which are quantitatively demonstrated by combined theoretical and experimental results. This finding provides fundamental insights into the origin of activity and selectivity over Cu-based catalysts and illustrates the value of our research framework in identifying active sites for complex heterogeneous catalysts.

Photocatalytic Performance of Carbon-Containing CuMo-Based Catalysts under Sunlight Illumination

“…A better cohesion between Cu species and the protective carbon layer may be due to a stronger oxidative role of ionic copper species [58] compared to ionic molybdenum species [59] according to Equations (3)- (8).…”

Exploring the adsorption site coordination as a strategy to tune copper catalysts for CO2 electro-reduction

“…Moreover, when comparing intermediates that could be related to reaction pathway bifurcations, we see that HCOO and CHO are more affected by the coordination than COOH and COH, which can lead to coordination-dependent pathways for different reactions as already observed in the literature. 48–50 Fig. 2 also shows through the magnitudes of the coefficient of determination, r 2 and the mean absolute error, MAE, that the GCN values can be used, to a certain extent, to explain the variation of E bind as a function of the adsorption site coordination.…”

Dynamics of Heterogeneous Catalytic Processes at Operando Conditions

“…(b) Proportions of different surface structures of the OD-Cu model. Reprinted from ref ( 181 ) under a Creative Commons CC BY License. (c) Snapshots from the MC simulation of a large (211) surface slab model with solvent, containing in total ∼6500 atoms.…”