文献类型：期刊文献

中文题名：The critical role of electrochemically activated adsorbates in neutral OER

英文题名：电化学活化吸附物对中性析氧反应的影响

作者：Longsheng Zhang[1];Haiyang Yuan[2];Liping Wang[1];Hui Zhang[3];Yijing Zang[3];Yao Tian[4];Yunzhou Wen[1];Fenglou Ni[1];Hao Song[4];Haifeng Wang[2];Bo Zhang[1];Huisheng Peng[1]

机构：[1]State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science and Laboratory of Advanced Materials,Fudan University,Shanghai 200438,China;[2]Key Laboratory for Advanced Materials,Key Laboratory for Advanced Materials,Centre for Computational Chemistry and Research Institute of Industrial Catalysis,East China University of Science and Technology,Shanghai 200237,China;[3]State Key Laboratory of Functional Materials for Informatics,Shanghai Institute of Microsystem and Information Technology,Chinese Academy of Sciences,CAS Center for Excellence in Superconducting Electronics,Shanghai 200050,China;[4]Key Laboratory of Systems Bioengineering,School of Chemical Engineering and Technology,SynBio Research Platform,Collaborative Innovation Centre of Chemical Science and Engineering,Tianjin University,Tianjin 300072,China

年份：2020

卷号：63

期号：12

起止页码：2509

中文期刊名：Science China Materials

外文期刊名：中国科学(材料科学(英文版)

收录：Scopus;CSCD:【CSCD2019_2020】；PubMed;

基金：This work was supported by the Ministry of Science and Technology (2016YFA0203302), the National Natural Science Foundation of China (21875042, 21634003, 51573027 and 11227902), Science and Technology Commission of Shanghai Municipality (16JC1400702 and 18QA1400800), Shanghai Municipal Education Commission (2017-01-07-00-07-E00062), Yanchang Petroleum Group, and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. This work also benefited from 1W1B beamline at Beijing Synchrotron Radiation Facility (BSRF) and BL02B01 beamline at Shanghai Synchrotron Radiation facility (SSRF).

语种：英文

中文关键词：electrocatalysis;oxygen evolution reaction;adsorbates;neutral electrolytes

外文关键词：密度泛函理论计算;吸附物;光电子能谱;低能离子散射谱;反应中间产物;反应动力学;析氧反应;电化学活化;

摘要：Developing efficient electrocatalysts for the oxygen evolution reaction(OER)under neutral conditions is important for microbial electrolysis cells(MECs).However,the OER kinetics in neutral electrolytes at present are extremely sluggish,resulting in high overpotentials that greatly limit the energy conversion efficiencies of MECs.Previous studies failed to probe the adsorbates on surface metal sites of catalysts at the atomic scale and elucidate their influence on the catalytic activities,which has impeded the rational design of efficient neutral OER catalysts with optimal surface structures.Here,using in situ transmission electron microscopy(TEM),in situ X-ray photoelectron spectroscopy(XPS)and in situ low-energy ion scattering studies,we have identified,for the first time,that the electrochemically activated adsorbates on surface metal sites play a critical role in boosting the neutral OER activities of Ru-Ir binary oxide(RuxIryO2)catalysts.The adsorbate-activated RuxIryO2on a glassy carbon electrode achieved a low overpotential of 324 m V at10 m A cm-2in neutral electrolyte,with a 36-fold improvement in turnover frequency compared with that of Ir O2benchmark.Upon application in an MEC system,the resulting full cell showed a decreased voltage of 1.8 V,200 m V lower than the best value reported to date,facilitating efficient synthesis of poly(3-hydroxybutyrate)from bioelectrochemical CO_(2)reduction.Density functional theory(DFT)studies revealed that the enhanced OER activity of RuxIryO2catalyst arose from local structural distortion of adjacent adsorbate-covered Ru octahedra at the catalyst surface and the consequently decreased adsorption energies of OER intermediates on Ir active center.
高效中性析氧催化剂在微生物电解池领域起着至关重要的作用.但是,目前中性析氧催化剂的过电位仍较高,其反应动力学极为缓慢.在本工作中,我们成功设计并制备了一种高效RuxIryO2催化剂,它兼具高析氧活性和高稳定性,其本征活性分别是商业RuO_(2)和Ir O2催化剂的7倍和36倍.我们进一步通过原位透射电子显微镜、光电子能谱和低能离子散射谱测试研究了RuxIryO2的表面吸附物对其催化活性的影响.结合密度泛函理论计算和实验结果,发现RuxIryO2催化剂中Ru位点被O*吸附物覆盖可提高其相邻Ir位点的催化活性.因为Jahn-Teller效应,当Ru–O键被削弱时,其相邻的Ir–O键会增强,从而减弱Ir位点对反应中间产物的吸附,最终提高RuxIryO2催化剂的析氧活性.