Ning Han, Shihui Feng, Yi Liang, Jun Wang, Wei Zhang, Xiaolong Guo, Qianru Ma, Qiong Liu, Wei Guo, Zhenyu Zhou, Sijie Xie, Kai Wan, Yinzhu Jiang, Alexandru Vlad, Yuzheng Guo, Eric M. Gaigneaux, Chi Zhang, Jan Fransaer, Xuan Zhang
{"title":"Achieving Efficient Electrocatalytic Oxygen Evolution in Acidic Media on Yttrium Ruthenate Pyrochlore through Cobalt Incorporation","authors":"Ning Han, Shihui Feng, Yi Liang, Jun Wang, Wei Zhang, Xiaolong Guo, Qianru Ma, Qiong Liu, Wei Guo, Zhenyu Zhou, Sijie Xie, Kai Wan, Yinzhu Jiang, Alexandru Vlad, Yuzheng Guo, Eric M. Gaigneaux, Chi Zhang, Jan Fransaer, Xuan Zhang","doi":"10.1002/adfm.202208399","DOIUrl":null,"url":null,"abstract":"<p>The development of electrocatalysts for the oxygen evolution reaction (OER) especially in acidic media remains the major challenge that still requires significant advances, both in material design and mechanistic exploration. In this study, the incorporation of cobalt in Y<sub>2-x</sub>Co<sub>x</sub>Ru<sub>2</sub>O<sub>7−δ</sub> results in an ultrahigh OER activity because of the charge redistribution at e<sub>g</sub> orbitals between Ru and Co atoms. The Y1.<sub>75</sub>Co<sub>0.25</sub>Ru<sub>2</sub>O<sub>7−δ</sub> electrocatalyst exhibits an extremely small overpotential of 275 mV in 0.5 <span>m</span> H<sub>2</sub>SO<sub>4</sub> at the current density of 10 mA cm<sup>−2</sup>, which is smaller than that of parent Y<sub>2</sub>Ru<sub>2</sub>O<sub>7−δ</sub> (360 mV) and commercial RuO<sub>2</sub> (286 mV) catalysts. The systematic investigation of the composition related to OER activity shows that the Co substitution will also bring other effective changes, such as reducing the bandgap, and creating oxygen vacancies, which result in fast OER charge transfer. Meanwhile, the strengthening of the bond hybridization between the d orbitals of metal (Y and Ru) and the 2p orbitals of O will intrinsically enhance the chemical stability. Finally, theoretical calculations indicate that cobalt substitution reduces the theoretical overpotential both through an adsorbate evolution mechanism and a lattice oxygen-mediated mechanism.</p>","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":18.5000,"publicationDate":"2023-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"17","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/adfm.202208399","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 17
Abstract
The development of electrocatalysts for the oxygen evolution reaction (OER) especially in acidic media remains the major challenge that still requires significant advances, both in material design and mechanistic exploration. In this study, the incorporation of cobalt in Y2-xCoxRu2O7−δ results in an ultrahigh OER activity because of the charge redistribution at eg orbitals between Ru and Co atoms. The Y1.75Co0.25Ru2O7−δ electrocatalyst exhibits an extremely small overpotential of 275 mV in 0.5 m H2SO4 at the current density of 10 mA cm−2, which is smaller than that of parent Y2Ru2O7−δ (360 mV) and commercial RuO2 (286 mV) catalysts. The systematic investigation of the composition related to OER activity shows that the Co substitution will also bring other effective changes, such as reducing the bandgap, and creating oxygen vacancies, which result in fast OER charge transfer. Meanwhile, the strengthening of the bond hybridization between the d orbitals of metal (Y and Ru) and the 2p orbitals of O will intrinsically enhance the chemical stability. Finally, theoretical calculations indicate that cobalt substitution reduces the theoretical overpotential both through an adsorbate evolution mechanism and a lattice oxygen-mediated mechanism.
发展出氧反应(OER)的电催化剂,特别是在酸性介质中,仍然是主要的挑战,仍然需要在材料设计和机理探索方面取得重大进展。在本研究中,由于Ru和Co原子之间在eg轨道上的电荷重新分布,在Y2-xCoxRu2O7−δ中掺入钴导致了超高的OER活性。Y1.75Co0.25Ru2O7−δ电催化剂在电流密度为10 mA cm−2时,在0.5 m H2SO4中表现出极小的过电位275 mV,小于母体Y2Ru2O7−δ (360 mV)和RuO2 (286 mV)催化剂的过电位。对OER活性相关成分的系统研究表明,Co取代还会带来其他有效的变化,如减小带隙和产生氧空位,从而导致OER电荷的快速转移。同时,金属(Y和Ru)的d轨道与O的2p轨道之间的键杂化的增强将从本质上提高化学稳定性。最后,理论计算表明,钴取代通过吸附质演化机制和晶格氧介导机制降低了理论过电位。
期刊介绍:
Firmly established as a top-tier materials science journal, Advanced Functional Materials reports breakthrough research in all aspects of materials science, including nanotechnology, chemistry, physics, and biology every week.
Advanced Functional Materials is known for its rapid and fair peer review, quality content, and high impact, making it the first choice of the international materials science community.