Affiliation:
1. Key Lab of Advanced Energy Storage and Conversion Zhejiang Province Key Lab of Leather Engineering College of Chemistry and Materials Engineering Wenzhou University Wenzhou Zhejiang 325035 China
2. Zhejiang Engineering Research Center for Electrochemical Energy Materials and Devices Institute of New Materials and Industrial Technologies Zhejiang- Canada Joint Laboratory on Energy Storage and electrocatalysis Wenzhou University Wenzhou Zhejiang 325035 China
3. International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education Institute of Microscale Optoelectronics Shenzhen University Shenzhen 518060 China
4. Department of Chemistry and Biochemistry University of Windsor Windsor Ontario N9B 3P4 Canada
Abstract
AbstractThe electrochemical CO2 reduction reaction (CO2RR) to generate chemical fuels such as formate presents a promising route to a carbon‐neutral future. However, its practical application is hindered by the competing CO production and hydrogen evolution reaction (HER), as well as the lack of pH‐universal catalysts. Here, Te‐modified Bi nanorods (Te−Bi NRs) were synthesized through in situ reconstruction of Bi2Te4O11 NRs under the CO2RR condition. Our study illustrates that the complex reconstruction process of Bi2Te4O11 NRs during CO2RR could be decoupled into three distinct steps, i.e., the destruction of Bi2Te4O11, the formation of Te/Bi phases, and the dissolution of Te. The thus‐obtained Te−Bi NRs exhibit remarkably high performance in CO2RR towards formate production, showing high activity, selectivity, and stability across all pH conditions (acidic, neutral, and alkaline). In a flow cell reactor under neutral, alkaline, or acidic conditions, the catalysts achieved HCOOH Faradaic efficiencies of up to 94.3 %, 96.4 %, and 91.0 %, respectively, at a high current density of 300 mA cm−2. Density functional theory calculations, along with operando spectral measurements, reveal that Te manipulates the Bi sites to an electron‐deficient state, enhancing the adsorption strength of the *OCHO intermediate, and significantly suppressing the competing HER and CO production. This study highlights the substantial influence of catalyst reconstruction under operational conditions and offers insights into designing highly active and stable electrocatalysts towards CO2RR.