Reactivity of Cr species grafted on SiO2/Si(100) surface:: A reflection extended X-ray absorption fine structure study down to the submonolayer regime

被引:20
作者
Agostini, G.
Groppo, E.
Bordiga, S.
Zecchina, A.
Prestipino, C.
D'Acapito, F.
van Kimmenade, E.
Thune, P. C.
Niemantsverdriet, J. W.
Lamberti, C.
机构
[1] Univ Turin, Dept Inorgan Phys & Mat Chem, I-10125 Turin, Italy
[2] Univ Turin, NIS Ctr Excellence, I-10125 Turin, Italy
[3] ESRF, F-38043 Grenoble, France
[4] ESRF, OGG, INFM, CNR, F-38043 Grenoble, France
[5] Eindhoven Univ Technol, Schuit Inst Catalysis, NL-5600 MB Eindhoven, Netherlands
关键词
D O I
10.1021/jp074066t
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
In situ X-ray absorption near-edge spectroscopy/extended X-ray absorption fine structure (XANES/EXAFS) experiments are conducted. for the first time on a highly diluted Cr/SiO2/Si(100) system (2 Cr/nm(2), representing a model of the Phillips catalyst for the ethylene polymerization) by exploiting the reflection EXAFS (ReflEXAFS) geometry. This experiment, aimed to give a contribution in bridging the gap between surface science and catalysis, demonstrates that it is possible to follow the reversible red-ox reactivity of surface species grafted on a single well-defined surface, at a concentration limit that is far below the monolayer coverage level and for a highly sensitive sample. A further improvement on the impurity level of the ReflEXAFS chamber is however required in order to be able to follow in situ the polymerization reaction. Our results demonstrate that the red-ox ability of the isolated surface Cr species is not enough to make a polymerization active species.
引用
收藏
页码:16437 / 16444
页数:8
相关论文
共 82 条
[1]   A kinetic study of ethylene and 1-hexene homo- and copolymerization catalyzed by a silica-supported Cr(IV) complex: Evidence for propagation by a migratory insertion mechanism [J].
Ajjou, JAN ;
Scott, SL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (37) :8968-8976
[2]   Evolution of extraframework iron species in Fe silicalite 1. Effect of Fe content, activation temperature, and interaction with redox agents [J].
Berlier, G ;
Spoto, G ;
Bordiga, S ;
Ricchiardi, G ;
Fisicaro, P ;
Zecchina, A ;
Rossetti, I ;
Selli, E ;
Forni, L ;
Giamello, E ;
Lamberti, C .
JOURNAL OF CATALYSIS, 2002, 208 (01) :64-82
[3]   MULTIELECTRON EXCITATIONS IN THE K-EDGE X-RAY-ABSORPTION NEAR-EDGE SPECTRA OF V, CR, AND MN 3D0 COMPOUNDS WITH TETRAHEDRAL COORDINATION [J].
BIANCONI, A ;
GARCIA, J ;
BENFATTO, M ;
MARCELLI, A ;
NATOLI, CR ;
RUIZLOPEZ, MF .
PHYSICAL REVIEW B, 1991, 43 (09) :6885-6892
[4]   Ti-peroxo species in the TS-1/H2O2/H2O system [J].
Bonino, F ;
Damin, A ;
Ricchiardi, G ;
Ricci, M ;
Spanò, G ;
D'Aloisio, R ;
Zecchina, A ;
Lamberti, C ;
Prestipino, C ;
Bordiga, S .
JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (11) :3573-3583
[5]   On the first stages of the ethylene polymerization on Cr2+/SiO2 Phillips catalyst:: time and temperature resolved IR studies [J].
Bordiga, S ;
Bertarione, S ;
Damin, A ;
Prestipino, C ;
Spoto, G ;
Lamberti, C ;
Zecchina, A .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2003, 204 :527-534
[6]   XAFS STUDY OF TI-SILICALITE - STRUCTURE OF FRAMEWORK TI(IV) IN THE PRESENCE AND ABSENCE OF REACTIVE MOLECULES (H2O, NH3) AND COMPARISON WITH ULTRAVIOLET-VISIBLE AND IR RESULTS [J].
BORDIGA, S ;
COLUCCIA, S ;
LAMBERTI, C ;
MARCHESE, L ;
ZECCHINA, A ;
BOSCHERINI, F ;
BUFFA, F ;
GENONI, F ;
LEOFANTI, G ;
PETRINI, G ;
VLAIC, G .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (15) :4125-4132
[7]   Reactivity of Ti(IV) species hosted in TS-1 towards H2O2-H2O Solutions investigated by ab initio cluster and periodic approaches combined with experimental XANES and EXAFS data:: a review and new highlights [J].
Bordiga, Silvia ;
Bonino, Francesca ;
Damin, Alessandro ;
Lamberti, Carlo .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2007, 9 (35) :4854-4878
[8]   STRUCTURAL INVESTIGATIONS OF ADSORBED LAYERS USING SYNCHROTRON RADIATION [J].
BRADSHAW, AM .
FARADAY DISCUSSIONS, 1990, 89 :1-20
[9]   Catalytic cleavage of the C-H and C-C bonds of alkanes by surface organometallic chemistry: An EXAFS and IR characterization of a Zr-H catalyst [J].
Corker, J ;
Lefebvre, F ;
Lecuyer, C ;
Dufaud, V ;
Quignard, F ;
Choplin, A ;
Evans, J ;
Basset, JM .
SCIENCE, 1996, 271 (5251) :966-969
[10]   Probing the initial stages of solid-state reactions by total reflection EXAFS (reflEXAFS) [J].
d'Acapito, F ;
Ghigna, P ;
Alessandri, I ;
Cardelli, A ;
Davoli, I .
NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS, 2003, 200 :421-424