Polyacrylamide‐Mediated Silver Nanoparticles for Selectively Enhancing Electroreduction of CO2 towards CO in Water

Abstract Conversion of the greenhouse gas CO 2 to value‐added products is an important challenge for sustainable energy research. Here, a durably nanohybrid composed of Ag nanoparticles and polyacrylamide was constructed for the selectively electroreduction of CO 2 to CO. The nanohybrid exhibited an outstanding CO faradaic efficiency of 97.2±0.2 % at −0.89 V RHE (vs. the reversible hydrogen electrode) with a desirable CO partial current density of −22.0±2.3 mA cm −2 and maintained the CO faradaic efficiency above 95 % over a wide potential range (−0.79 to −1.09 V RHE ), showing excellent stability during a 48 h prolonged electrolysis. The origins of selective enhancement of CO 2 reduction over the nanohybrid stemmed from the activation of CO 2 via hydrogen bond and the low basicity of the amide. DFT calculations implied that the synergy of Ag nanoparticles and amide could better stabilize the key intermediate (*COOH) and effectively lower the overpotential of CO 2 reduction. These results establish the synergistic effects of organic/inorganic hybrid as a complementary method for tuning selectivity in CO 2 ‐to‐fuels catalysis.