Zhenjie Li, Zhonghui Hu, Yuanqing Wang and Runhai Ouyang*,
{"title":"共-铁基包晶石氧化物/水界面的分子动力学模拟","authors":"Zhenjie Li, Zhonghui Hu, Yuanqing Wang and Runhai Ouyang*, ","doi":"10.1021/acs.jpcc.4c03394","DOIUrl":null,"url":null,"abstract":"<p >Perovskite oxides have shown promising catalytic performances in the oxygen evolution reaction (OER), yet the intricate reconstruction at the oxide/electrolyte interfaces has complicated the understanding of the catalytic mechanism and hindered the rational design of catalysts. In this work, molecular dynamics (MD) simulations of perovskite oxide/water interfaces were performed based on on-the-fly machine learning potentials to provide atomistic insights into the influence of solvent on surface structure of the prototypical oxides Ba<sub>0.5</sub>Sr<sub>0.5</sub>Co<sub>0.75</sub>Fe<sub>0.25</sub>O<sub>3</sub> (BSCF) and Rb<sub>0.25</sub>Sr<sub>0.75</sub>Co<sub>0.5</sub>Fe<sub>0.5</sub>O<sub>3</sub> (RSCF). Results show that water plays important roles in many structural phenomena, in particular on transition metal-terminated surfaces. The presence of water facilitates the dynamic oxygen exchange between that in the lattice and that in water via the H–O bonding. Formation of surface peroxo species and gas O<sub>2</sub> molecules was observed, leaving tetragonal [CoO<sub>4</sub>H] surface units in each of which one oxygen is stabilized by forming the O–H bond. In addition, we found that the oxygens bonded to Co atoms are responsible for nearly all of the observed lattice-oxygen-related events due to the weaker bonding of O with Co than with Fe. In comparison to BSCF, no peroxo species and gas O<sub>2</sub> molecules were observed within the same simulation time length on RSCF because of the lower content of Co. These findings highlight the roles of water in surface reconstruction and the importance of Co for the reactivity of lattice oxygen.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"128 24","pages":"10035–10041"},"PeriodicalIF":3.2000,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Molecular Dynamics Simulation of Co–Fe-Based Perovskite Oxide/Water Interfaces\",\"authors\":\"Zhenjie Li, Zhonghui Hu, Yuanqing Wang and Runhai Ouyang*, \",\"doi\":\"10.1021/acs.jpcc.4c03394\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Perovskite oxides have shown promising catalytic performances in the oxygen evolution reaction (OER), yet the intricate reconstruction at the oxide/electrolyte interfaces has complicated the understanding of the catalytic mechanism and hindered the rational design of catalysts. In this work, molecular dynamics (MD) simulations of perovskite oxide/water interfaces were performed based on on-the-fly machine learning potentials to provide atomistic insights into the influence of solvent on surface structure of the prototypical oxides Ba<sub>0.5</sub>Sr<sub>0.5</sub>Co<sub>0.75</sub>Fe<sub>0.25</sub>O<sub>3</sub> (BSCF) and Rb<sub>0.25</sub>Sr<sub>0.75</sub>Co<sub>0.5</sub>Fe<sub>0.5</sub>O<sub>3</sub> (RSCF). Results show that water plays important roles in many structural phenomena, in particular on transition metal-terminated surfaces. The presence of water facilitates the dynamic oxygen exchange between that in the lattice and that in water via the H–O bonding. Formation of surface peroxo species and gas O<sub>2</sub> molecules was observed, leaving tetragonal [CoO<sub>4</sub>H] surface units in each of which one oxygen is stabilized by forming the O–H bond. In addition, we found that the oxygens bonded to Co atoms are responsible for nearly all of the observed lattice-oxygen-related events due to the weaker bonding of O with Co than with Fe. In comparison to BSCF, no peroxo species and gas O<sub>2</sub> molecules were observed within the same simulation time length on RSCF because of the lower content of Co. These findings highlight the roles of water in surface reconstruction and the importance of Co for the reactivity of lattice oxygen.</p>\",\"PeriodicalId\":61,\"journal\":{\"name\":\"The Journal of Physical Chemistry C\",\"volume\":\"128 24\",\"pages\":\"10035–10041\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-06-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry C\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpcc.4c03394\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry C","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpcc.4c03394","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
包晶氧化物在氧进化反应(OER)中表现出良好的催化性能,然而氧化物/电解质界面错综复杂的重构使人们对催化机理的理解变得复杂,并阻碍了催化剂的合理设计。在这项工作中,基于即时机器学习势能对包晶氧化物/水界面进行了分子动力学(MD)模拟,从而从原子角度深入了解了溶剂对原型氧化物 Ba0.5Sr0.5Co0.75Fe0.25O3 (BSCF) 和 Rb0.25Sr0.75Co0.5Fe0.5O3 (RSCF) 表面结构的影响。研究结果表明,水在许多结构现象中发挥着重要作用,尤其是在过渡金属表面。水的存在通过 H-O 键促进了晶格中的氧和水中的氧之间的动态交换。我们观察到表面过氧物种和气体 O2 分子的形成,并在每个单元中留下四方 [CoO4H] 表面单元,其中一个氧通过形成 O-H 键而得到稳定。此外,我们还发现,由于 O 与 Co 的键合作用比与 Fe 的键合作用弱,因此与 Co 原子键合的氧几乎是所有观察到的晶格氧相关事件的原因。这些发现突出了水在表面重构中的作用以及 Co 对晶格氧反应性的重要性。
Molecular Dynamics Simulation of Co–Fe-Based Perovskite Oxide/Water Interfaces
Perovskite oxides have shown promising catalytic performances in the oxygen evolution reaction (OER), yet the intricate reconstruction at the oxide/electrolyte interfaces has complicated the understanding of the catalytic mechanism and hindered the rational design of catalysts. In this work, molecular dynamics (MD) simulations of perovskite oxide/water interfaces were performed based on on-the-fly machine learning potentials to provide atomistic insights into the influence of solvent on surface structure of the prototypical oxides Ba0.5Sr0.5Co0.75Fe0.25O3 (BSCF) and Rb0.25Sr0.75Co0.5Fe0.5O3 (RSCF). Results show that water plays important roles in many structural phenomena, in particular on transition metal-terminated surfaces. The presence of water facilitates the dynamic oxygen exchange between that in the lattice and that in water via the H–O bonding. Formation of surface peroxo species and gas O2 molecules was observed, leaving tetragonal [CoO4H] surface units in each of which one oxygen is stabilized by forming the O–H bond. In addition, we found that the oxygens bonded to Co atoms are responsible for nearly all of the observed lattice-oxygen-related events due to the weaker bonding of O with Co than with Fe. In comparison to BSCF, no peroxo species and gas O2 molecules were observed within the same simulation time length on RSCF because of the lower content of Co. These findings highlight the roles of water in surface reconstruction and the importance of Co for the reactivity of lattice oxygen.
期刊介绍:
The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.