针对吸附剂机理计算 pH 值 12 和 pH 值 14 之间氧进化反应的塔菲尔斜率和反应阶次

IF 2.9 Q2 ELECTROCHEMISTRY Electrochemical science advances Pub Date : 2022-11-25 DOI:10.1002/elsa.202100213
Denis Antipin, Marcel Risch
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引用次数: 0

摘要

尽管针对氧进化反应(OER)进行了大量实验和理论研究,但过渡金属氧化物上的 OER 机理仍存在争议。部分原因是该机理的电化学参数(如塔菲尔斜率和反应阶数)不明确。我们采用了最常见的吸附机理假设,并基于稳态近似的微动力学分析,计算了塔菲尔斜率和反应阶数与 pH 值的关系。分析针对的是没有中间产物缩放的理想电催化剂,以及位于火山关系顶端的理想电催化剂和位于火山关系每条腿上的理想电催化剂,后者表现出中间产物的缩放。在这四种情况下,可能的塔菲尔斜率数量在很大程度上取决于表面覆盖率。此外,当中间产物的覆盖率随 pH 值变化时,塔菲尔斜率也会随 pH 值变化而变化。这些见解使在单一 pH 值下通过单一塔菲尔斜率确定限速步骤的工作变得复杂。然而,与塔菲尔斜率互补的反应顺序模拟可以解决一些模糊问题,从而区分可能的限速步骤。从塔菲尔图的低过电位区域可以获得最有洞察力的信息。这项工作中的模拟为实验人员提供了明确的指导,使他们能够利用在 pH 依赖性研究中观察到的塔菲尔斜率值和反应阶次来确定吸附机理中的限制步骤。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Calculation of the Tafel slope and reaction order of the oxygen evolution reaction between pH 12 and pH 14 for the adsorbate mechanism

Despite numerous experimental and theoretical studies devoted to the oxygen evolution reaction (OER), the mechanism of the OER on transition metal oxides remains controversial. This is in part owing to the ambiguity of electrochemical parameters of the mechanism such as the Tafel slope and reaction orders. We took the most commonly assumed adsorbate mechanism and calculated the Tafel slopes and reaction orders with respect to pH based on microkinetic analysis using the steady-state approximation. The analysis was performed for an ideal electrocatalyst without scaling of the intermediates as well as for one on the top of a volcano relation and one on each leg of the volcano relation which exhibits scaling of the intermediates. For these four cases, the number of possible Tafel slopes strongly depends on surface coverage. Furthermore, the Tafel slope becomes pH-dependent when the coverage of intermediates changes with pH. These insights complicate the identification of a rate-limiting step by a single Tafel slope at a single pH. Yet, simulations of reaction orders complementary to Tafel slopes can solve some ambiguities to distinguish between possible rate-limiting steps. The most insightful information can be obtained from the low overpotential region of the Tafel plot. The simulations in this work provide clear guidelines to experimentalists for the identification of the limiting steps in the adsorbate mechanism using the observed values of the Tafel slope and reaction order in pH-dependent studies.

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