Highly Selective CO Electroreduction to CH Using a Metal-Organic Framework with Dual Active Sites.

Conversion from CO to CH is important for the development of energy and the environment, but the high energy barrier of hydrogenation of the *CO intermediate and C-C coupling step tend to result in C compounds as the main product and thus restrict the generation of CH. Here, we report a metal-organic framework (denoted as ), composed of 2,3,9,10,16,17,23,24-octahydroxyphthalo-cyaninato)copper(II) (PcCu-(OH)) ligands and the square-planar CuO nodes, as the electrocatalyst for CO to CH. Compared with the discrete molecular copper-phthalocyanine (Faradaic efficiency (FE) of CH = 25%), exhibits much higher performance for electrocatalytic reduction of CO to CH with a FE of 50(1)% and a current density of 7.3 mA cm at the potential of -1.2 V vs RHE in 0.1 M KHCO solution, representing the best performance reported to date. infrared spectroscopy and control experiments suggested that the enhanced electrochemical performance may be ascribed to the synergistic effect between the CuPc unit and the CuO unit, namely the CO on the CO-producing site (CuO site) can efficiently migrate and dimerize with the *CO intermediate adsorbed on the CH-producing site (CuPc), giving a lower C-C dimerization energy barrier.