image: Potential/confinement effect can play an important role on electrochemical steps by changing the (electro)chemical potential of electron. As a result, potential-dependent energetics and TS structures are essential for a more accurate description of reaction mechanism and activity. view more
Credit: Chinese Journal of Catalysis
As the green and sustainable development of human society highly relies on renewable energy, it has been recognized that electrocatalysis is a key technology to this end. Advanced theoretical study is an important means to fundamentally understanding electrocatalytic reactions. High-efficient ways of carbon-neutralization (eCO2RR), reverse artificial nitrogen cycle (RANC), and oxygen chemistry (OER and ORR) all can be driven by electrocatalysis. The computational hydrogen electrode (CHE) model developed by Nørskov et.al can describe the influence of electrode potential on the reaction free energies, by shifting the chemical potential of proton-electron couple. It has been widely used for estimating the thermodynamics in electrocatalysis.
The study of interfacial kinetics is vital for the understanding of catalytic reaction and design of catalysts. Calculating the potential-dependent barriers of a proton-electron coupled transfer reaction is an important step of microkinetic modelling in electrocatalysis. The charge-extrapolation method based on the capacitor model can easily and accurately obtain the barrier under a specific potential, so as to fully consider the influence of the electrode potential on the reaction. The interface microenvironment can also affect surface reactions, and considering the competition among multiple paths can provide a more inclusive understanding.
In this perspective, a research team led by Prof. Jianping Xiao from Dalian Institute of Chemical Physics, CAS summarized the efforts towards calculating potential-dependent barriers on the basis of charge-extrapolation method. Electrochemical barriers and potential effects are essential for a more accurate description of reaction mechanism and activity. Meanwhile, consideration of competitive reaction paths is also one of the important aspects, as novel insights and anomalous volcano trend can be obtained. Finally, confined microenvironment shows a possibility of tuning the capacitance at water-electrode interface, resulting in a possibility to improve reaction activity, which can opens a new avenue for electrode design in electrocatalysis. The perspective was published in Chinese Journal of Catalysis (DOI: 10.1016/S1872-2067(22)64090-7).
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About the Journal
Chinese Journal of Catalysis is co-sponsored by Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Chinese Chemical Society, and it is currently published by Elsevier group. This monthly journal publishes in English timely contributions of original and rigorously reviewed manuscripts covering all areas of catalysis. The journal publishes Reviews, Accounts, Communications, Articles, Highlights, Perspectives, and Viewpoints of highly scientific values that help understanding and defining of new concepts in both fundamental issues and practical applications of catalysis. Chinese Journal of Catalysis ranks among the top two journals in Applied Chemistry with a current SCI impact factor of 12.92. The Editors-in-Chief are Profs. Can Li and Tao Zhang.
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