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The electrochemical reduction of CO2 to HCOOH is considered one of the most appealing routes to alleviate the energy crisis and close the anthropogenic CO2 cycle. However, it remains challenging to develop electrocatalysts with high activity and selectivity towards HCOOH in a wide potential window. In this regard, Ag/Bi2O2CO3 was prepared by an in situ electrochemical transformation from Ag/Bi2O3. The Ag/Bi2O2CO3 catalyst achieves a faradaic efficiency (FE) of over 90% for HCOOH in a wide potential window between −0.8 V and −1.3 V versus the reversible hydrogen electrode (RHE). Moreover, a maximum FE of 95.8% and a current density of 15.3 mA cm−2 were achieved at a low applied potential of −1.1 V. Density functional theory (DFT) calculations prove that the high catalytic activity of Ag/Bi2O2CO3 is ascribed to the fact that Ag can regulate the electronic structure of Bi, thus facilitating the adsorption of *OCHO and hindering the adsorption of *COOH. This work expands the in situ electrochemical derivatization strategy for the preparation of electrocatalysts. [ABSTRACT FROM AUTHOR]

A nanosheet catalyst with Cu0/Cu+ interfaces, derived from in-situ electroreduction of CuO NS, enhances the adsorption of *OCCOH intermediate, thus reducing the energy barrier of C C coupling and conducive to the formation of C 2+ products. [Display omitted] Electrochemical carbon dioxide reduction reaction (CO 2 RR) is an effective approach to capture CO 2 and convert it into value-added chemicals and fuels, thereby reducing excess CO 2 emissions. Recent reports have shown that copper-based catalysts exhibit excellent performance in converting CO 2 into multi-carbon compounds and hydrocarbons. However, the selectivity to the coupling products is poor. Therefore, tuning CO 2 -reduction selectivity toward C 2+ products over Cu-based catalyst is one of the most important issues in CO 2 RR. Herein, we prepare a nanosheet catalyst with interfaces of Cu0/Cu+. The catalyst achieves Faraday efficiency (FE) of C 2+ over 50% in a wide potential window between − 1.2 V to − 1.5 V versus reversible hydrogen electrode (vs. RHE). Moreover, the catalyst exhibits maximum FE of 44.5% and 58.9% towards C 2 H 4 and C 2+ , with a partial current density of 10.5 mA cm−2 at − 1.4 V. Density functional theory (DFT) calculations show that the interface of Cu0/Cu+ facilitates C C coupling to form C 2+ products, while inhibits CO 2 conversion to C 1 products. [ABSTRACT FROM AUTHOR]