Abstract

Engineering the electronic properties of catalysts to target intermediate adsorption energy as well as harvest high selectivity represents a promising strategy to design advanced electrocatalysts for efficient CO2 electroreduction. Herein, a synergistically tuning on the electronic structure of the CdSe nanorods is proposed for boosting electrochemical reduction of CO2. The synergy of Ag doping coupled with Se vacancies tuned the electronic structure of the CdSe nanorods, which shows the metalloid characterization and thereby the accelerated electron transfer of CO2 electroreduction. Operando synchrotron radiation Fourier transform infrared spectroscopy and theoretical simulation revealed that the Ag doping and Se vacancies accelerated the CO2 activation process and lowered the energy barrier for the conversion from CO2 to *COOH; as a result, the performance of CO2 electroreduction was enhanced. The as-obtained metalloid Ag-doped CdSe nanorods exhibited a 2.7-fold increment in current density and 1.9-fold Faradaic efficiency of CO than pristine CdSe nanorod.

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