The Reconstruction of Bi₂Te₄O₁₁ Nanorods for Efficient and pH-universal Electrochemical CO₂ Reduction

The 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.