Boosting Electrochemical Reduction of CO₂ to Formate over Oxygen Vacancy Stabilized Copper–Tin Dual Single Atoms Catalysts

Abstract

Designing reasonable atomic structures is essential in modulating the selectivity of the valuable products produced in the electrochemical CO2 reduction. Herein, a CuSn diatomic sites electrocatalyst stabilized by double oxygen vacancies on CeO2‐x is constructed, which exhibits superior electrochemical selectivity toward formate, achieving a 90.0% Faradaic efficiency at formate partial current density of 216.8 mA cm−2 with the applied bias of −1.2 V versus REH. The experimental characterizations and theoretical calculations highlight the significance of the synergistic effect of Cu and Sn diatoms on reducing the activation energy and promoting the formation of intermediate *OCHO, which accounts for its high selectivity toward formate. Meanwhile, the oxygen vacancies on the CeO2‐x also play a pivotal role in manipulating the electrochemical performance and stability, which underlines the importance of regulating the electronic metal‐support interaction between CuSn diatoms and CeO2‐x. This work demonstrates an effective method to design efficient electrochemical CO2 reduction catalysts by modulating the surface structures of single‐atoms anchored support.

Recent advances of metal suboxide catalysts for carbon‐neutral energy applications

“…Currently, various methods have been proposed to convert CO 2 into value‐added products, including chemical transformation, photocatalytic reduction, electrocatalytic reduction and biological conversion. Among them, the electrocatalytic CRR has been regarded as one of the most promising pathways for CO 2 conversion 32,161,162 . These products included C 1 products such as carbon monoxide (CO), formic acid (HCOOH), methane (CH 4 ), and methyl alcohol (CH 3 OH), as well as C 2 products like ethylene (C 2 H 4 ), ethane (C 2 H 6 ), ethyl alcohol (CH 3 CH 2 OH), and acetic acid (CH 3 COOH), and C 3 and C 3+ products 32,163 .…”

Advances and challenges in the electrochemical reduction of carbon dioxide

“…7a and b ). 96 Besides, a sacrificial protection strategy to stabilize the interfacial crystalline CuO by embedding active amorphous SnO 2 (c-CuO/a-SnO 2 ) was reported by Guo et al DFT calculations demonstrated that the loss of oxygen in the heterostructure mainly originates from amorphous SnO 2 , avoiding the reduction of c-CuO. Meanwhile, the production of O v in c-SnO 2 leads to off-domain s-orbital electrons around the tin atom, which provides additional electrons in higher orbitals than the unoccupied d-orbitals of Cu 2+ ( Fig.…”

Steady Cu+ species via magnesium and boron co-modification for enhanced CO2 electroreduction to C2+ products: an in situ Raman spectroscopic study

“…The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) represents a pathway for producing high-value-added chemicals and fuels, offering a means to reduce global carbon dioxide (CO 2 ) emissions and alleviate the shortage of non-renewable carbon resources. 1–3 The CO 2 RR yields primarily hydrocarbons and oxygen-containing compounds. Among them, multi-carbon (C 2+ ) products such as ethylene (C 2 H 4 ) and ethanol (C 2 H 5 OH) have broader industrial applications and higher energy densities compared with C 1 products like carbon monoxide (CO) and methane (CH 4 ), thus commanding a higher economic value per unit mass.…”