文献类型：期刊文献

英文题名：Importing Antibonding-Orbital Occupancy through Pd-O-Gd Bridge Promotes Electrocatalytic Oxygen Reduction

作者：Ning, Shuwang[1] Li, Meng[1] Wang, Xuan[1] Zhang, Di[4] Zhang, Baiyu[1] Wang, Caikang[1] Sun, Dongmei[1] Tang, Yawen[1] Li, Hao[4] Sun, Kang[2,3] Fu, Gengtao[1]

第一作者：Ning, Shuwang

通信作者：Fu, GT[1];Sun, K[2];Sun, K[3]

机构：[1]Nanjing Normal Univ, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Sch Chem & Mat Sci, Jiangsu Key Lab New Power Batteries, Nanjing 210023, Peoples R China;[2]Chinese Acad Forestry, Inst Chem Ind Forest Prod, Key Lab Biomass Energy & Mat, 16 Suojin 5th Village, Nanjing 210042, Jiangsu, Peoples R China;[3]Chinese Acad Sci, Xinjiang Tech Inst Phys & Chem, Key Lab Funct Mat & Devices Special Environm, 40-1 South Beijing Rd, Urumqi 830011, Xinjiang, Peoples R China;[4]Tohoku Univ, Adv Inst Mat Res WPI AIMR, Sendai 9808577, Japan

年份：2023

卷号：62

期号：52

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20234715094275);Scopus(收录号：2-s2.0-85177183827);WOS:【SCI-EXPANDED(收录号:WOS:001105753900001)】；

基金：This work was financially supported by the Foundation of Jiangsu Key Lab of Biomass Energy and Material (JSBEM-S-202101), National Natural Science Foundation of China (22379071, 22109073 and 22072067), Natural Science Foundation of Jiangsu Province (BK20221321), Jiangsu Specially Appointed Professor Plan, Science and Technology Innovation Project for Overseas Researchers in Nanjing, JSPS KAKENHI (No. JP23K13703), and the Iwatani Naoji Foundation. The authors are grateful for the support from the National and Local Joint Engineering Research Center of Biomedical Functional Materials and a project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions. H.L. acknowledges the Center for Computational Materials Science, Institute for Materials Research, Tohoku University for the use of MASAMUNE-IMR (No. 202212-SCKXX-0204) and the Institute for Solid State Physics (ISSP) at the University of Tokyo for the use of their supercomputers.

语种：英文

外文关键词：Gadolinium; Metal-Organic Framework; Oxygen Reduction Reaction; Palladium; Rare Earth Oxides

摘要：The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon-based rare-earth (RE) oxides (Gd2O3, Sm2O3, Eu2O3, and CeO2) by using RE metal-organic frameworks to tune the ORR performance of the Pd sites through the Pd-RExOy interface interaction. Taking Pd-Gd2O3/C as a representative, it is identified that the strong coupling between Pd and Gd2O3 induces the formation of the Pd-O-Gd bridge, which triggers charge redistribution of Pd and Gd2O3. The screened Pd-Gd2O3/C exhibits impressive ORR performance with high onset potential (0.986 VRHE), half-wave potential (0.877 VRHE), and excellent stability. Similar ORR results are also found for Pd-Sm2O3/C, Pd-Eu2O3/C, and Pd-CeO2/C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2O3 promotes electron transfer through the Pd-O-Gd bridge, which induces the antibonding-orbital occupancy of Pd-*OH for the optimization of *OH adsorption in the rate-determining step of ORR. The pH-dependent microkinetic modeling shows that Pd-Gd2O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd-Gd2O3/C exhibits superior performance in Zn-air battery as an air cathode, implying its excellent practicability. This work constructs a series of carbon-based rare-earth oxides via an RE metal-organic framework-mediated strategy to tune the ORR performance of the Pd sites. Taking Pd-Gd2O3/C as a representative, it is identified that the coupling between Pd and Gd2O3 promotes electron transfer through the Pd-O-Gd bridge, which induces the antibonding-orbital occupancy of Pd-*OH for the optimization of *OH adsorption in the rate-determining step of ORR.+image