文献类型：期刊文献

英文题名：Interaction of Hydrogen with Ceria: Hydroxylation, Reduction, and Hydride Formation on the Surface and in the Bulk

作者：Li, Zhaorui[1,2];Werner, Kristin[3];Chen, Lu[4,5,6];Jia, Aiping[1,2,7];Qian, Kun[1,2];Zhong, Jian-Qiang[3];You, Rui[1,2];Wu, Lihui[8];Zhang, Liyuan[1,2];Pan, Haibin[8];Wu, Xin-Ping[4,5,6];Gong, Xue-Qing[4,5,6];Shaikhutdinov, Shamil[3];Huang, Weixin[1,2,9];Freund, Hans-Joachim[3]

机构：[1]Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Key Lab Surface & Interface Chem & Energy Catalys, CAS Key Lab Mat Energy Convers, Hefei 230026, Peoples R China;[2]Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Peoples R China;[3]Max Planck Gesell, Fritz Haber Inst, Faradayweg 4-6, D-14195 Berlin, Germany;[4]East China Univ Sci & Technol, Key Lab Adv Mat, Feringa Nobel Prize Scientist Joint Res Ctr, Ctr Computat Chem,Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Ctr Computat Chem,Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[6]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[7]Zhejiang Normal Univ, Inst Phys Chem, Minist Educ Adv Catalysis Mat, Key Lab, Jinhua 321004, Zhejiang, Peoples R China;[8]Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Peoples R China;[9]Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China

年份：2021

卷号：27

期号：16

起止页码：5268

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：;EI(收录号：20210809950930);WOS:【SCI-EXPANDED(收录号:WOS:000618977800001)】；

基金：This work is financially supported by National Key R&D Program of MOST (2017YFB0602205), the DFG-NSFC joint project (Nos. FR554/18-1 and 21761132005), the National Natural Science Foundation of China (91945301, 21525313, 91745202, U1930203, 21825301), the Chinese Academy of Sciences, and the Changjiang Scholars Program of Ministry of Education of China. H.J.F. thanks Fonds der Chemischen Industrie. J.Q.Z. thanks the AvH Foundation for a fellowship. Open access funding enabled and organized by Projekt DEAL.

语种：英文

外文关键词：ceria; density functional calculations; hydride; hydrogenation; surface structure

摘要：The study reports the first attempt to address the interplay between surface and bulk in hydride formation in ceria (CeO2) by combining experiment, using surface sensitive and bulk sensitive spectroscopic techniques on the two sample systems, i.e., CeO2(111) thin films and CeO2 powders, and theoretical calculations of CeO2(111) surfaces with oxygen vacancies (O-v) at the surface and in the bulk. We show that, on a stoichiometric CeO2(111) surface, H-2 dissociates and forms surface hydroxyls (OH). On the pre-reduced CeO2-x samples, both films and powders, hydroxyls and hydrides (Ce-H) are formed on the surface as well as in the bulk, accompanied by the Ce3+ <-> Ce4+ redox reaction. As the O-v concentration increases, hydroxyl is destabilized and hydride becomes more stable. Surface hydroxyl is more stable than bulk hydroxyl, whereas bulk hydride is more stable than surface hydride. The surface hydride formation is the kinetically favorable process at relatively low temperatures, and the resulting surface hydride may diffuse into the bulk region and be stabilized therein. At higher temperatures, surface hydroxyls can react to produce water and create additional oxygen vacancies, increasing its concentration, which controls the H-2/CeO2 interaction. The results demonstrate a large diversity of reaction pathways, which have to be taken into account for better understanding of reactivity of ceria-based catalysts in a hydrogen-rich atmosphere.