Molecular Stabilization of Sub-Nanometer Cu Clusters for Selective CO2 Electromethanation

Graphical Lend me your EORs : Electrochemical oxidation-reduction (EOR) processing of a Cu-based metal-organic framework results in the formation of sub-nanometer Cu clusters that retains the organic linkers for highly selective and durable electrosynthesis of methane from the electrochemical CO 2 reduction reaction. Electrochemical CO 2 methanation powered by renewable electricity provides a promising approach to utilizing CO 2 in the form of a high-energy-density, clean fuel. Cu nanoclusters have been predicted by theoretical calculations to improve methane selectivity. Direct electrochemical reduction of Cu-based metal-organic frameworks (MOFs) results in large-size Cu nanoparticles which favor multi-carbon products. This study concerns an electrochemical oxidation-reduction method to prepare Cu clusters from MOFs. The derived Cu clusters exhibit a faradaic efficiency of 51.2 % for CH 4 with a partial current density of >150 mA cm −2 . High-resolution microscopy, in situ X-ray absorption spectroscopy, in situ Raman spectroscopy, and a range of ex situ spectroscopies indicate that the distinctive CH 4 selectivity is due to the sub-nanometer size of the derived materials, as well as stabilization of the clusters by residual ligands of the pristine MOF. This work offers a new insight into steering product selectivity of Cu by an electrochemical processing method.