Self-Polarization Triggered Multiple Polar Units Toward Electrochemical Reduction of CO 2 to Ethanol with High Selectivity.

Electrochemical conversion of CO 2 to highly valuable ethanol has been considered a intriguring strategy for carbon neutruality. However, the slow kinetics of coupling carbon-carbon (C-C) bonds, especially the low selectivity ethanol than ethylene in neutral conditions, is a significant challenge. Herein, the asymmetrical refinement structure with enhanced charge polarization is built in the vertically oriented bimetallic organic frameworks (NiCu-MOF) nanorod array with encapsulated Cu 2 O (Cu 2 O@MOF/CF), which can induce an intensive internal electric field to increase the C-C coupling for producing ethanol in neutral electrolyte. Particularly, when directly employed Cu 2 O@MOF/CF as the self-supporting electrode, the ethanol faradaic efficiency (FE ethanol ) could reach maximum 44.3 % with an energy efficiency of 27 % at a low working-potential of -0.615 V versus the reversible hydrogen electrode (vs. RHE) using CO 2 -saturated 0.5 M KHCO 3 as the electrolyte. Experimental and theoretical studies suggest that the polarization of atomically localized electric fields derived from the asymmetric electron distribution can tune the moderate adsorption of *CO to assist the C-C coupling and reduce the formation energy of H 2 CCHO*-to-*OCHCH 3 for the generation of ethanol. Our research offers a reference for the design of highly active and selective electrocatalysts for reducing CO 2 to multicarbon chemicals.