Cho Jinwon, Alamgir Faisal M, Jang Seung Soon
School of Materials Science and Engineering, Georgia Institute of Technology, 771 Ferst Dr., Atlanta, GA, 30332-0245, United States.
Computational Science Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado, 80401, United States.
ChemSusChem. 2025 Feb 1;18(3):e202401673. doi: 10.1002/cssc.202401673. Epub 2024 Nov 5.
Understanding the influence of local electric fields on electrochemical reactions is crucial for designing highly selective electrocatalysts for CO reduction reactions (CORR). In this study, we provide a theoretical investigation of the effect of the local electric field induced by the negative-biased electrode and cations in the electrolyte on the energetics and reaction kinetics of CORR on 2D hybrid metal/graphene electrocatalysts. Our findings reveal that the electronic structures of the CO molecule undergo substantial modification, resulting in the increased adsorption energy of CO on metal/graphene structures, thus reducing the initial barrier of the CORR mechanism. This field-assisted CORR mechanism promotes CO production while suppressing HCOOH production. Our findings highlight the potential of manipulating electric fields to tailor the pathways of CORR, providing new avenues designing selective electrocatalysts.
了解局部电场对电化学反应的影响对于设计用于CO还原反应（CORR）的高选择性电催化剂至关重要。在本研究中，我们对由负偏压电极和电解质中的阳离子诱导的局部电场对二维混合金属/石墨烯电催化剂上CORR的能量学和反应动力学的影响进行了理论研究。我们的研究结果表明，CO分子的电子结构发生了显著变化，导致CO在金属/石墨烯结构上的吸附能增加，从而降低了CORR机理的初始势垒。这种场辅助CORR机理促进了CO的生成，同时抑制了HCOOH的生成。我们的研究结果突出了操纵电场以定制CORR路径的潜力，为设计选择性电催化剂提供了新途径。
