Crystalline-Amorphous Interfaces Engineering of CoO-InOx for Highly Efficient CO2 Electroreduction to CO.

As a fundamental product of CO2 conversion through two-electron transfer, CO is used to produce numerous chemicals and fuels with high efficiency, which has broad application prospects. In this work, it has successfully optimized catalytic activity by fabricating an electrocatalyst featuring crystalline-amorphous CoO-InOx interfaces, thereby significantly expediting CO production. The 1.21%CoO-InOx consists of randomly dispersed CoO crystalline particles among amorphous InOx nanoribbons. In contrast to the same-phase structure, the unique CoO-InOx heterostructure provides plentiful reactive crystalline-amorphous interfacial sites. The Faradaic efficiency of CO (FECO) can reach up to 95.67% with a current density of 61.72 mA cm-2 in a typical H-cell using MeCN containing 0.5 M 1-Butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6) as the electrolyte. Comprehensive experiments indicate that CoO-InOx interfaces with optimization of charge transfer enhance the double-layer capacitance and CO2 adsorption capacity. Theoretical calculations further reveal that the regulating of the electronic structure at interfacial sites not only optimizes the Gibbs free energy of *COOH intermediate formation but also inhibits HER, resulting in high selectivity toward CO.

Dual-metal sites drive tandem electrocatalytic CO2 to C2+ products.

The electrochemical conversion of CO2 into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C2+) products is highly desired. Here, we report a 1.4%Pd-Cu@CuPz2 comprising of dispersive CuOx and PdO dual nanoclusters embedded in the MOF CuPz2 (Pz = Pyrazole), which achieves a high C2+ Faradaic efficiency (FEC2+) of 81.9% and C2+ alcohol FE of 47.5% with remarkable stability when using 0.1 M KCl aqueous solution as electrolyte in a typical H-cell. Particularly, the FE of alcohol is obviously improved on 1.4%Pd-Cu@CuPz2 compared to Cu@CuPz2. Theoretical calculations have revealed that revealed that the enhanced interfacial electron transfer facilitates the adsorption of *CO intermediate and *CO-*CO dimerization on the Cu-Pd dual sites bridged by Cu nodes of CuPz2. Additionally, the oxophilicity of Pd can stabilize the key intermediate *CH2CHO and promote subsequent proton-coupled electron transfer more efficiently, confirming that the formation pathway is skew towards *C2H5OH. Consequently, the Cu-Pd dual sites play a synergistic tandem role in cooperatively improving the selectivity of alcohol and accelerating reductive conversion of CO2 to C2+.