波动分析法解释均相催化剂的电催化伏安法及其更广泛的意义,ACS Catalysis

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波动分析法解释均相催化剂的电催化伏安法及其更广泛的意义
ACS Catalysis ( IF 11.3 ) Pub Date : 2019-06-21 00:00:00 , DOI: 10.1021/acscatal.9b00850
Vincent C.-C. Wang ₁ , Ben A. Johnson ₂

Affiliation

电催化反应的机理研究在开发有效的电催化剂和太阳能设备方面起着至关重要的作用。Savéant和Costentin最近开发了用于循环伏安法的波动分析（FOWA）脚，它为评估分子电催化剂的性能提供了强大的手段。但是，在如何解释多电子电化学反应中的FOWA方面，社区存在相当多的困惑。在此，我们进一步将其较早的模型从能斯特地区扩展到所有场景（即包括非能斯特行为），并系统地检查各个参数，例如形式势和反应速率常数，以探索更深刻的见解和局限性。来自silico的详细分析基于不同机理模型的伏安图揭示了针对不同动力学现象的FOWA迹线的特征，这对于诊断动力学轮廓和阐明FOWA的局限性很有用。从这些分析中吸取的教训可进一步用于调和FOWA与其他方法（例如时间分辨光谱法）确定的速率常数对催化质子还原或CO ₂还原的分子电催化剂的差异。这种对账表明，电化学方法与FOWA一起可以用作确定动力学信息和探查机理见解的替代工具，否则，采用常规方法很难实现，而且难度很大。此外，还提供了一般准则和警告，以避免在使用FOWA时可能出现的错误或处理不当。

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Interpreting the Electrocatalytic Voltammetry of Homogeneous Catalysts by the Foot of the Wave Analysis and Its Wider Implications

Mechanistic studies of electrocatalytic reactions play a crucial role in developing efficient electrocatalysts and solar-fuel devices. The foot of the wave analysis (FOWA) for cyclic voltammetry, recently developed by Savéant and Costentin, provides a powerful means to evaluate the performance of molecular electrocatalysts. However, there is a considerable amount of confusion in the community on how to interpret FOWA in multielectron electrochemical reactions. Herein, we further expand their earlier models from the Nernstian region to all scenarios (i.e., including non-Nernstian behavior) and systematically examine individual parameters, such as formal potentials and reaction rate constants, to explore deeper insights and limitations. Detailed analysis from in silico voltammograms based on different mechanistic models reveals characteristic features of FOWA traces for different kinetic phenomena, which is useful to diagnose kinetic profiles and elucidate the limits of FOWA. The lessons learned from these analyses are further used to reconcile the discrepancy of rate constants determined by FOWA versus other methods, such as time-resolved spectroscopy, for molecular electrocatalysts that catalyze proton reduction or the reduction of CO₂ to CO. Such reconciliation demonstrates that electrochemical methods along with FOWA can serve as an alternative tool to determine kinetic information and probe mechanistic insights, which otherwise may be challenging and complicated to achieve by conventional methods. In addition, general guidelines and warnings are also presented to avoid potential errors or mishandling when using FOWA.

更新日期：2019-06-21

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