Low-Valence Znδ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO2 Reduction

Electrochemical CO2 reduction represents a promising approach to sustainably produce carbon-based chemicals and fuels but has been experiencing challenges in developing low-cost and efficient electrocatalysts. Herein, a nitrogen-stabilized single-atom catalyst containing low-valence zinc atoms (Znδ+-NC) is reported. It is revealed that Znδ+-NC contains a mixture of saturated four-coordinate (Zn-N4) and unsaturated three-coordinate (Zn-N3) sites. The latter makes Zn a low-valence state, as deduced from X-ray photoelectron spectroscopy, X-ray absorption fine structure spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) simulation. As a result, Znδ+-NC catalyzes electrochemical reduction of CO2 to CO with near-unity selectivity in water at an overpotential as low as 310 mV. Importantly, a record-high current density up to 1 A cm-2 can be achieved together with high CO selectivity of >95% using Znδ+-NC in a flow cell reactor. DFT calculations suggest that the unsaturated Zn-N3 site could dramatically reduce the energy barrier by stabilizing the COOH* (* represents active sites) intermediate due to the electron-rich environment of Zn. This work not only sheds light on the relationship among coordination number, valence state, and catalytic performance of Zn single-atom sites, but also succeeds in achieving high current densities relevant for industrial applications.