Dicopper(I) Sites Confined in a Single Metal-Organic Layer Boosting the Electroreduction of CO2 to CH4 in a Neutral Electrolyte.

It is challenging and important to achieve high performance for an electrochemical CO2 reduction reaction (eCO2RR) to yield CH4 under neutral conditions. So far, most of the reported active sites for eCO2RR to yield CH4 are single metal sites; the performances are far below the commercial requirements. Herein, we reported a nanosheet metal-organic layer in single-layer, namely, [Cu2(obpy)2] (Cuobpy-SL, Hobpy = 1H-[2,2']bipyridinyl-6-one), possessing dicopper(I) sites for eCO2RR to yield CH4 in a neutral aqueous solution. Detailed examination of Cuobpy-SL revealed high performance for CH4 production with a faradic efficiency of 82(1)% and a current density of ∼90 mA cm-2 at -1.4 V vs. reversible hydrogen electrode (RHE). No obvious degradation was observed over 100 h of continuous operation, representing a remarkable performance to date. Mechanism studies showed that compared with the conventional single-copper sites and completely exposed dicopper(I) sites, the dicopper(I) sites in the confined space formed by the molecular stacking have a strong affinity to key C1 intermediates such as *CO, *CHO, and *CH2O to facilitate the CH4 production, yet inhibiting C-C coupling.