Copper Nanowires for Electrochemical CO₂ Reduction Reaction

Abstract

A promising carbon capture and utilization strategy is the electrochemical reduction of CO 2 (eCO 2 R) to value-added chemicals. Critical to the success of this approach is the development of catalysts capable of selectively converting aqueous CO 2 into a specific product. Copper (Cu) is considered the best pure metal candidate for eCO 2 R for its ability to catalyze the formation of several hydrocarbons, aldehydes, and alcohols. However, Cu lacks the required selectivity. In this regard, a finetuned control of its surface topology and nanostructuring could allow the enhancement of eCO 2 R catalysis. Here, we report a computational investigation of the growth tendency of Cu nanowires (NWs) as well as their ability to adsorb, activate, and convert CO 2 to one-and two-carbon products to understand their potential application as eCO 2 R catalysts. Grand canonical Monte Carlo simulations of the growth of Cu nanowires with diameters between 0.8 to 2 nm showed the tendency to form regular nanowires with a facet center cubic unit cell pattern. Cu nanowires demonstrated a pronounced propensity to activate CO 2 , particularly those with a 0.8 nm diameter, owing to the markedly uncoordinated Cu atoms on the surface and higher d-band center, which effectively promotes CO 2 interaction with the surface, molecule bending, C−O bond elongation, and charge transfer from the catalyst to CO 2 . Calculation of the CO 2 conversion to C 1 products shows the Cu NWs to be highly selective to carbon monoxide, a key intermediate ion in the generation of C 2 products.

Electrocatalytic CO2 Reduction on Amorphous Cu Surfaces: Unveiling Structure-Activity Relationships

“…These sites exhibit CNs ranging from 5 to 9, as illustrated in Fig. 6 Recent DFT studies suggest that the reduction of CO to *CHO, followed by its coupling with another *CO to form COCHO, is a more favorable pathway compared to CO dimerization [50], [51], [52], [53]. This is corroborated by the low energy…”