Sequentially Regulating Potential-Determining Step for Lowering CO2 Electroreduction Overpotential over Te-Doped Bi Nanotips.
Angew Chem Int Ed Engl
; 63(36): e202407772, 2024 Sep 02.
Article
en En
| MEDLINE
| ID: mdl-38872256
ABSTRACT
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 (-0.57â
V to -1.08â
V). The strong Bi-Te covalent bonds also afford a robust stability. In an optimized membrane electrode assembly device, the formate production rate at 3.2â
V reaches 10.1â
mmol h-1 cm-2, demonstrating great potential for practical application.
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MEDLINE
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En
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Angew Chem Int Ed Engl
Año:
2024
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Article