Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO2 Conversion to One Carbon Products

Abstract

Electrochemical CO2 reduction reactions can lead to high value-added chemical and materials production while helping decrease anthropogenic CO2 emissions. Copper metal clusters can reduce CO2 to more than thirty different hydrocarbons and oxygenates yet they lack the required selectivity. We present a computational characterization of the role of nano-structuring and alloying in Cu-based catalysts on the activity and selectivity of CO2 reduction to generate the following one-carbon products: carbon monoxide (CO), formic acid (HCOOH), formaldehyde (H2C=O), methanol (CH3OH) and methane (CH4). The structures and energetics were determined for the adsorption, activation, and conversion of CO2 on monometallic and bimetallic (decorated and core@shell) 55-atom Cu-based clusters. The dopant metals considered were Ag, Cd, Pd, Pt, and Zn, located at different coordination sites. The relative binding strength of the intermediates were used to identify the optimal catalyst for the selective CO2 conversion to one-carbon products. It was discovered that single atom Cd or Zn doping is optimal for the conversion of CO2 to CO. The core@shell models with Ag, Pd and Pt provided higher selectivity for formic acid and formaldehyde. The Cu-Pt and Cu-Pd showed lowest overpotential for methane formation.

A systematic theoretical study of CO2 hydrogenation towards methanol on Cu-based bimetallic catalysts: role of the CHO&CH3OH descriptor in thermodynamic analysis

“…3 Currently, commercial catalysts for methanol production are primarily based on low-cost and high-activity copper materials. Based on this, the copper-based bimetallic catalysts, such as Au-Cu, 4 Ni-Cu, 5,6 Pd-Cu, 7,8 Pt-Cu 9 and Zn-Cu, 10,11 can enhance methanol production with higher selectivity at lower temperatures, addressing the sintering and deactivation issues. However, in previous studies, there has been limited comprehensive exploration of multiple bimetallic alloy combinations under the same computational standards.…”

CO2 and H2 Activation on Zinc‐Doped Copper Clusters

“…[19] Recently, Density Functional Theory (DFT) and Neural Network potential based high throughput screening of CuZn model nanoparticle active sites showed the synergistic effect of the copper-zinc for CO binding, what facilitates the C 2 + product formation. [20] It has also been concluded using DFT computations that the icosahedral Cu 54 Zn or Cu 54 Cd are optimal for the electrochemical conversion of CO 2 to CO. [21] Gas-phase cluster models might provide valuable insight into the molecular processes in catalysis, as it has been shown e. g. for CO oxidation catalyzed by small gas phase palladium cluster cations. [22] Pd n + showed similar reaction paths for this reaction to that on extended surfaces, however the energetics was different, and particularly, Pd 6…”

“…Recently, Density Functional Theory (DFT) and Neural Network potential based high throughput screening of CuZn model nanoparticle active sites showed the synergistic effect of the copper‐zinc for CO binding, what facilitates the C 2+ product formation [20] . It has also been concluded using DFT computations that the icosahedral Cu 54 Zn or Cu 54 Cd are optimal for the electrochemical conversion of CO 2 to CO [21] …”