Theoretical and Experimental Study of the Effects of Cobalt and Nickel Doping within IrO2 on the Acidic Oxygen Evolution Reaction
Theoretical and Experimental Study of the Effects of Cobalt and Nickel Doping within IrO2 on the Acidic Oxygen Evolution Reaction
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DOI：
10.1016/j.jcat.2022.02.016
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发表时间：
2022-02
影响因子：
7.3
通讯作者：
Luis E. Camacho-Forero;F. Godínez-Salomón;G. Ramos-Sánchez;Christopher P. Rhodes;P. Balbuena
中科院分区：
文献类型：
--
作者：
Luis E. Camacho-Forero;F. Godínez-Salomón;G. Ramos-Sánchez;Christopher P. Rhodes;P. Balbuena
采用理论与实验相结合的方法研究了iro2ni和Co掺杂对其结构和析氧反应（OER）的影响。密度泛函理论（DFT）计算表明，与未掺杂的IrO2相比，金属掺杂影响了电子电荷的分布，影响了OER的热力学和动力学方面。利用DFT，对O-O键形成的多种不同反应途径进行了评估，分析支持缔合机制是最可能的反应途径。计算表明，与未掺杂的IrO2相比，Ni和共掺杂的IrO2的活化能较低，与实验分析的活化能和OER活度一致。实验表明，与ni掺杂相比，共掺杂明显提高了稳定性。从计算和实验分析中对速率决定步长（rds）的评估显示出明显的差异，这表明需要考虑其他因素，以改善OER rds的理论和实验之间的相关性。
The effect of Ni and Co doping within IrO2on the structure and oxygen evolution reaction (OER) was studied using integrated theory and experiments. Density Functional Theory (DFT) calculations show that the metal dopant influences the distribution of electronic charge and affects the thermodynamics and kinetics aspects of the OER when compared with undoped IrO2. Using DFT, multiple different reaction pathways were evaluated for O-O bond formation, and analysis supports the associative mechanism to be the most likely reaction pathway. Calculations showed lower activation energies for Ni and Co-doped IrO2compared to undoped IrO2, in agreement with experimental analysis of the activation energy and OER activity. From experiments, Co-doping shows significantly improved stability compared to Ni-doping. Evaluation of the rate-determining step (rds) from calculations and experimental analysis shows apparent differences that indicate the additional factors need to be considered to enable improved correlation between theory and experiment regarding the OER rds.