Asymmetric Local Electric Field Induced by Dual Heteroatoms on Copper Boosts Efficient CO2 Reduction Over Ultrawide Potential Window

• Published in: Angewandte Chemie International Edition Vol. 63; no. 37; pp. e202407661 - n/a
• Main Authors: Xie, Feng, Wang, Zhen, Kao, Cheng‐Wei, Lan, Jiao, Lu, Ying‐Rui, Tan, Yongwen
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 09.09.2024
• Edition: International ed. in English
• Subjects: Aqueous solutions; asymmetric local electric field; Asymmetry; Carbon dioxide; Catalysts; Chemical reduction; Copper; Copper converters; Density functional theory; Electric fields; Electric potential; Electrochemical CO2 reduction reaction; Energy efficiency; Gold; Hydrogen evolution reactions; nanoporous; Silver; Spectroscopy; Tin
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202407661

Electrocatalytic reduction of CO2 powered by renewable electricity provides an elegant route for converting CO2 into valuable chemicals and feedstocks, but normally suffers from a high overpotential and low selectivity. Herein, Ag and Sn heteroatoms were simultaneously introduced into nanoporous Cu (np‐Ag/Sn−Cu) mainly in the form of an asymmetric local electric field for CO2 electroreduction to CO in an aqueous solution. The designed np‐Ag/Sn−Cu catalyst realizes a recorded 90 % energy efficiency and a 100 % CO Faradaic efficiency over ultrawide potential window (ΔE=1.4 V), outperforming state‐of‐the‐art Au and Ag‐based catalysts. Density functional theory calculations combined with in situ spectroscopy studies reveal that Ag and Sn heteroatoms incorporated into Cu matrix could generate strong and asymmetric local electric field, which promotes the activation of CO2 molecules, enhances the stabilization of the *COOH intermediate, and suppresses the hydrogen evolution reaction, thus favoring the production of CO during CO2RR. Silver and tin heteroatoms are injected into the nano‐porous copper to construct an asymmetric local electric field, thereby realizing excellent selectivity up to a nearly 100 % Faraday efficiency for CO over ultrawide potential window, a superior CO local current density of 340 mA cm−2 at −1.6 V versus reversible hydrogen electrode and high energy efficiency of 90 % for CO production.