In Situ XANES/XPS Investigation of Doped Manganese Perovskite Catalysts

被引:72
作者
Mierwaldt, Daniel [1 ]
Mildner, Stephanie [1 ]
Arrigo, Rosa [2 ]
Knop-Gericke, Axel [2 ]
Franke, Emanuel [1 ]
Blumenstein, Andreas [1 ]
Hoffmann, Joerg [1 ]
Jooss, Christian [1 ]
机构
[1] Univ Gottingen, Inst Mat Phys, D-37077 Gottingen, Germany
[2] Max Planck Gesell, Fritz Haber Inst, D-14195 Berlin, Germany
来源
CATALYSTS | 2014年 / 4卷 / 02期
关键词
catalysis; oxygen evolution; manganese perovskite; Pr1-xCaxMnO3; XANES; XPS; Mn L-edge; active state; oxygen vacancies; surface valence; X-RAY-ABSORPTION; PULSED-LASER DEPOSITION; NEAR-EDGE STRUCTURE; MIXED-VALENCE; OXIDATION-STATES; SPECTROSCOPY; MN; OXIDES; MANGANITES; BEHAVIOR;
D O I
10.3390/catal4020129
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Studying catalysts in situ is of high interest for understanding their surface structure and electronic states in operation. Herein, we present a study of epitaxial manganite perovskite thin films (Pr1-xCaxMnO3) active for the oxygen evolution reaction (OER) from electro-catalytic water splitting. X-ray absorption near-edge spectroscopy (XANES) at the Mn L- and O K-edges, as well as X-ray photoemission spectroscopy (XPS) of the O 1s and Ca 2p states have been performed in ultra-high vacuum and in water vapor under positive applied bias at room temperature. It is shown that under the oxidizing conditions of the OER a reduced Mn2+ species is generated at the catalyst surface. The Mn valence shift is accompanied by the formation of surface oxygen vacancies. Annealing of the catalysts in O-2 atmosphere at 120 degrees C restores the virgin surfaces.
引用
收藏
页码:129 / 145
页数:17
相关论文
共 38 条
[1]   CONTROLLED-VALENCE PROPERTIES OF LA1-XSRXFEO3 AND LA1-XSRXMNO3 STUDIED BY SOFT-X-RAY ABSORPTION-SPECTROSCOPY [J].
ABBATE, M ;
DEGROOT, FMF ;
FUGGLE, JC ;
FUJIMORI, A ;
STREBEL, O ;
LOPEZ, F ;
DOMKE, M ;
KAINDL, G ;
SAWATZKY, GA ;
TAKANO, M ;
TAKEDA, Y ;
EISAKI, H ;
UCHIDA, S .
PHYSICAL REVIEW B, 1992, 46 (08) :4511-4519
[2]   Influence of the synthetic pathway on the properties of oxygen-deficient manganese-related perovskites [J].
Alonso, Jose M. ;
Cortes-Gil, Raquel ;
Ruiz-Gonzalez, Luisa ;
Gonzalez-Calbet, Jose M. ;
Hernando, Antonio ;
Vallet-Regi, Maria ;
Davila, Maria E. ;
Asensio, Maria C. .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2007, (21) :3350-3355
[3]   Why did nature choose manganese to make oxygen? [J].
Armstrong, Fraser A. .
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY B-BIOLOGICAL SCIENCES, 2008, 363 (1494) :1263-1270
[4]  
Blochl P., 2014, 1 PRINCIPLES S UNPUB
[5]   Trends in Stability of Perovskite Oxides [J].
Calle-Vallejo, Federico ;
Martinez, Jose I. ;
Garcia-Lastra, Juan M. ;
Mogensen, Mogens ;
Rossmeisl, Jan .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (42) :7699-7701
[6]   Surfaces of the perovskite manganites La1-xCaxMnO3 [J].
Choi, JW ;
Zhang, JD ;
Liou, SH ;
Dowben, PA ;
Plummer, EW .
PHYSICAL REVIEW B, 1999, 59 (20) :13453-13459
[7]   LIGAND-FIELD STRENGTHS AND OXIDATION-STATES FROM MANGANESE L-EDGE SPECTROSCOPY [J].
CRAMER, SP ;
DEGROOT, FMF ;
MA, Y ;
CHEN, CT ;
SETTE, F ;
KIPKE, CA ;
EICHHORN, DM ;
CHAN, MK ;
ARMSTRONG, WH ;
LIBBY, E ;
CHRISTOU, G ;
BROOKER, S ;
MCKEE, V ;
MULLINS, OC ;
FUGGLE, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :7937-7940
[8]   USE OF L-EDGE X-RAY-ABSORPTION SPECTROSCOPY TO CHARACTERIZE MULTIPLE VALENCE STATES OF 3D TRANSITION-METALS - A NEW PROBE FOR MINERALOGICAL AND GEOCHEMICAL RESEARCH [J].
CRESSEY, G ;
HENDERSON, CMB ;
VANDERLAAN, G .
PHYSICS AND CHEMISTRY OF MINERALS, 1993, 20 (02) :111-119
[9]   2P X-RAY ABSORPTION OF 3D TRANSITION-METAL COMPOUNDS - AN ATOMIC MULTIPLET DESCRIPTION INCLUDING THE CRYSTAL-FIELD [J].
DEGROOT, FMF ;
FUGGLE, JC ;
THOLE, BT ;
SAWATZKY, GA .
PHYSICAL REVIEW B, 1990, 42 (09) :5459-5468
[10]   OXYGEN 1S X-RAY-ABSORPTION EDGES OF TRANSITION-METAL OXIDES [J].
DEGROOT, FMF ;
GRIONI, M ;
FUGGLE, JC ;
GHIJSEN, J ;
SAWATZKY, GA ;
PETERSEN, H .
PHYSICAL REVIEW B, 1989, 40 (08) :5715-5723