Ab Initio Thermodynamics and Kinetics of the Lattice Oxygen Evolution Reaction in Iridium Oxides
Ab Initio Thermodynamics and Kinetics of the Lattice Oxygen Evolution Reaction in Iridium Oxides
复制标题
氧化铱晶格析氧反应的从头算热力学和动力学
DOI：
10.1021/acsenergylett.1c00234
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发表时间：
2021
影响因子：
22
通讯作者：
Alexandrov, Vitaly
中科院分区：
文献类型：
--
作者：
Zagalskaya, Alexandra;Evazzade, Iman;Alexandrov, Vitaly
氧化铱基催化剂是酸性介质中阳极析氧反应（OER）最活跃和最稳定的材料之一，但它们的寿命也是一个重要问题。最近，许多过渡金属氧化物的研究表明，OER 中晶格氧原子的积极参与会影响催化剂的稳定性。在这项工作中，我们结合基于密度泛函理论的热力学和分子动力学来分析一系列含铱氧化物的OER活性。我们发现，尽管一些 Ir 氧化物在传统反应途径中表现出的热力学超电势低于最先进的 IrO2 金红石，但它们还具有晶格氧原子向 OER 方向同时活化的特点。通过关注一些代表性案例，我们明确地证明了晶格氧机制由于其较低的动力学势垒而可以优于传统机制。由于晶格氧的演化与氧化物降解在实验上相关，因此由于晶格氧的参与而增强的 OER 活性会损害材料的稳定性。这项研究强调了考虑晶格析氧反应对于电化学稳定的 OER 催化剂的更可靠的计算预测的重要性。
Iridium-oxide-based catalysts are among the most active and stable materials for the anodic oxygen evolution reaction (OER) in acidic media, but even their longevity represents an important issue. It was recently demonstrated for many transition-metal oxides that stability of a catalyst can suffer from the active participation of lattice oxygen atoms in the OER. In this work, we combine density functional theory-based thermodynamics and molecular dynamics to analyze the OER activity of a series of Ir-bearing oxides. We reveal that although some Ir oxides exhibit thermodynamic overpotentials lower than that of the state-of-the-art IrO2rutile for the conventional reaction pathway, they also feature concomitant activation of lattice oxygen atoms toward the OER. By focusing on a few representative cases we unequivocally demonstrate that the lattice oxygen mechanism can outperform the conventional mechanism owing to its lower kinetic barriers. As lattice oxygen evolution was experimentally correlated with oxide degradation, enhanced OER activity due to involvement of lattice oxygen should compromise materials stability. This study highlights the importance of considering the lattice oxygen evolution reaction for more reliable computational predictions of electrochemically stable OER catalysts.
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影响因子：
5.3
作者：
Cherevko, Serhiy;Geiger, Simon;Mayrhofer, Karl J. J.
通讯作者：
Mayrhofer, Karl J. J.
影响因子：
37.8
作者：
Hong Nhan Nong;Reier, Tobias;Strasser, Peter
通讯作者：
Strasser, Peter
高强度激光与簇介质相互作用产生的激光驱动辐射爆炸波
DOI：
--
发表时间：
2016
期刊：
影响因子：
--
作者：
加藤郁也;脇坂優美;南本大穂;村越 敬;福田祐仁
通讯作者：
福田祐仁
影响因子：
15
作者：
McCrory, Charles C. L.;Jung, Suho;Jaramillo, Thomas F.
通讯作者：
Jaramillo, Thomas F.