Sequentially Regulating Potential-Determining Step for Lowering CO₂ Electroreduction Overpotential over Te-Doped Bi Nanotips

Electrocatalytic conversion of CO₂ into formate is recognized an economically-viable route to upgrade CO₂, but requires high overpotential to realize the high selectivity owing to high energy barrier for driving the involved proton-coupled electron transfer (PCET) processes and serious ignorance of the second PCET. Herein, we surmount the challenge through sequential regulation of the potential-determining step (PDS) over Te-doped Bi (TeBi) nanotips. Computational studies unravel the incorporation of Te heteroatoms alters the PDS from the first PCET to the second one by substantially lowering the formation barrier for *OCHO intermediate, and the high-curvature nanotips induce enhanced electric field that can steer the formation of asymmetric *HCOOH. In this scenario, the thermodynamic barrier for *OCHO and *HCOOH can be sequentially decreased, thus enabling a high formate selectivity at low overpotential. Experimentally, distinct TeBi nanostructures are obtained via controlling Te content in the precursor and TeBi nanotips achieve >90 % of Faradaic efficiency for formate production over a comparatively positive potential window (−0.57 V to −1.08 V). The strong Bi−Te covalent bonds also afford a robust stability. In an optimized membrane electrode assembly device, the formate production rate at 3.2 V reaches 10.1 mmol h⁻¹ cm⁻², demonstrating great potential for practical application.