Inverted Region in Electrochemical Reduction of CO2 Induced by Potential-Dependent Pauli Repulsion,Journal of the American Chemical Society

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Inverted Region in Electrochemical Reduction of CO2 Induced by Potential-Dependent Pauli Repulsion
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-06-09 , DOI: 10.1021/jacs.3c02447
Leyu Liu ₁ , Hai Xiao ₁

Affiliation

Electrochemical CO₂ reduction reaction (eCO₂RR) is of great significance to energy and environmental engineering, while fundamental questions remain regarding its mechanisms. Herein, we formulate a fundamental understanding of the interplay between the applied potential (U) and kinetics of CO₂ activation in eCO₂RR on Cu surfaces. We find that the nature of the CO₂ activation mechanism in eCO₂RR varies with U, and it is the sequential electron–proton transfer (SEPT) mechanism dominant at the working U but switched to the concerted proton–electron transfer (CPET) mechanism at highly negative U. We then identify that the barrier of the electron-transfer step in the SEPT mechanism exhibits an inverted region as U decreases, which originates from the rapidly rising Pauli repulsion in the physisorption of CO₂ with decreasing U. We further demonstrate catalyst designs that effectively suppress the adverse effect of Pauli repulsion. This fundamental understanding may be general for the electrochemical reduction reactions of closed-shell molecules.

中文翻译：

电势相关泡利排斥引起的 CO2 电化学还原中的反转区域

电化学CO ₂还原反应(eCO ₂ RR)对于能源和环境工程具有重要意义，但其机理仍存在根本问题。在此，我们对铜表面eCO ₂ RR 中施加的电势 ( U ) 和 CO ₂活化动力学之间的相互作用有了基本的了解。我们发现eCO ₂ RR中CO ₂活化机制的性质随U的变化而变化，并且在工作U时是顺序电子-质子转移（SEPT）机制占主导地位，但切换到协同质子-电子转移（CPET）机制在高度负U。然后我们发现SEPT机制中电子转移步骤的势垒随着U的减小而呈现出反转区域，这源于随着U的减小CO ₂物理吸附中的泡利排斥力迅速上升。我们进一步证明了催化剂设计可以有效抑制泡利排斥的不利影响。这种基本理解对于闭壳分子的电化学还原反应可能是普遍的。

更新日期：2023-06-09

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