%0 Journal Article %@ 1613-6810 %A Palanimuthu, Naveenkumar %A Subramaniam, Mohan Raj %A Austeria P, Muthu %A Sharma, Preetam Kumar %A Ramalingam, Vinoth %A Peramaiah, Karthik %A Ramakrishnan, Shanmugam %A Gu, Geun Ho %A Yu, Eileen Hao %A Yoo, Dong Jin %D 2024 %F discovery:10197355 %I WILEY-V C H VERLAG GMBH %J Small %K Bismuth oxide; density functional theory; electrochemical CO2 reduction; formate; surface area %T Surface Area-Enhanced Cerium and Sulfur-Modified Hierarchical Bismuth Oxide Nanosheets for Electrochemical Carbon Dioxide Reduction to Formate %U https://discovery.ucl.ac.uk/id/eprint/10197355/ %X Electrochemical carbon dioxide reduction reaction (ECO2RR) is a promising approach to synthesize fuels and value-added chemical feedstocks while reducing atmospheric CO2 levels. Here, high surface area cerium and sulfur-doped hierarchical bismuth oxide nanosheets (Ce@S-Bi2O3) are develpoed by a solvothermal method. The resulting Ce@S-Bi2O3 electrocatalyst shows a maximum formate Faradaic efficiency (FE) of 92.5% and a current density of 42.09 mA cm−2 at −1.16 V versus RHE using a traditional H-cell system. Furthermore, using a three-chamber gas diffusion electrode (GDE) reactor, a maximum formate FE of 85% is achieved in a wide range of applied potentials (−0.86 to −1.36 V vs RHE) using Ce@S-Bi2O3. The density functional theory (DFT) results show that doping of Ce and S in Bi2O3 enhances formate production by weakening the OH* and H* species. Moreover, DFT calculations reveal that *OCHO is a dominant pathway on Ce@S-Bi2O3 that leads to efficient formate production. This study opens up new avenues for designing metal and element-doped electrocatalysts to improve the catalytic activity and selectivity for ECO2RR. %Z This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.