A Stable Metal-azolate Framework with Cyclic Tetracopper(I) Clusters for Highly Selective Electroreduction of CO 2 to C 2 Products.

It is of great significance for constructing electrocatalysts with accurate structures and compositions to pinpoint the active sites, thereby improving the C 2 products (C 2 H 4 , C 2 H 5 OH and CH 3 COOH) selectivity during electrocatalytic CO 2 reduction raction. Here, we report a tetracopper(I) cluster-based metal-organic framework that exhibits long-term stability and remarkable performance for electroreduction CO 2 towards C 2 products in an H-type cell with a maximum Faradaic efficiency (FE) of 72%, and delivers a current density of 350 mA cm -2 with a FE(C 2 ) up to 46% in a flow cell device, outperforming most of the Cu-based electrocatalysts such as Cu derivatives and Cu nanostructured materials. Importantly, no obvious degradation was observed at 350 mA cm -2 over 20 hours of continuous operation, strengthening the practicability. In-situ infrared spectroscopy analysis showed the cooperative effect of adjacent Cu(I) ions in tetracopper(I) cluster may promote the C-C coupling to generate C 2 products.