Activation of Oxygen on MgO: O2•- Radical Ion Formation on Thin, Metal-Supported MgO(001) Films

被引：95

作者：

Gonchar, Anastasia ^{[2
]}

Risse, Thomas ^{[2
,3
]}

Freund, Hans-Joachim ^{[2
]}

Giordano, Livia ^{[1
]}

Di Valentin, Cristiana ^{[1
]}

Pacchioni, Gianfranco ^{[1
]}

机构：

[1] Univ Milano Bicocca, Dipartimento Sci Mat, I-20125 Milan, Italy

[2] Max Planck Gesell, Fritz Haber Inst, Dept Chem Phys, D-14195 Berlin, Germany

[3] Free Univ Berlin, Inst Chem & Biochem, D-14195 Berlin, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 11期

关键词：

heterogeneous catalysis; oxidation; oxygen activation; surface chemistry; thin films; PARAMAGNETIC-RESONANCE; SURFACE; EXCHANGE; DENSITY; ATOMS; MODEL;

D O I：

10.1002/anie.201005729

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Distortion is the key: In situ EPR spectroscopy provides the first experimental confirmation that the adsorption of O2 molecules on a stoichiometric ultrathin MgO(001) film on Mo(001) leads to the spontaneous formation of O2.- radicals. The results show that polaronic distortion of the MgO lattice (see picture; Mg yellow, O blue) stabilizes the radical, and this distortion is only possible in very thin films. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：2635 / 2638

页数：4

共 26 条

[11] PARAMAGNETIC RESONANCE OF OXYGEN IN ALKALI HALIDES [J].

KANZIG, W ;

COHEN, MH .

PHYSICAL REVIEW LETTERS, 1959, 3 (11) :509-510

[12] Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J].

Kresse, G ;

Furthmuller, J .

PHYSICAL REVIEW B, 1996, 54 (16) :11169-11186

[13] ABINITIO MOLECULAR-DYNAMICS FOR LIQUID-METALS [J].

KRESSE, G ;

HAFNER, J .

PHYSICAL REVIEW B, 1993, 47 (01) :558-561

[14] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].

LEE, CT ;

YANG, WT ;

PARR, RG .

PHYSICAL REVIEW B, 1988, 37 (02) :785-789

[15] Formation of Superoxo Species by Interaction of O2 with Na Atoms Deposited on MgO Powders: A Combined Continuous-Wave EPR (CW-EPR), Hyperfine Sublevel Correlation (HYSCORE) and DFT Study [J].

Napoli, Francesco ;

Chiesa, Mario ;

Giamello, Elio ;

Preda, Gloria ;

Di Valentin, Cristiana ;

Pacchioni, Gianfranco .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (23) :6776-6785

[16] Prediction of electron paramagnetic resonance g values using coupled perturbed Hartree-Fock and Kohn-Sham theory [J].

Neese, F .

JOURNAL OF CHEMICAL PHYSICS, 2001, 115 (24) :11080-11096

[17] Charging of metal atoms on ultrathin MgO/Mo(100) films [J].

Pacchioni, G ;

Giordano, L ;

Baistrocchi, M .

PHYSICAL REVIEW LETTERS, 2005, 94 (22)

[18] Cluster model of O-2(-) adsorption on regular and defect sites and F-s centers of the MgO(100) surface [J].

Pacchioni, G ;

Ferrari, AM ;

Giamello, E .

CHEMICAL PHYSICS LETTERS, 1996, 255 (1-3) :58-64

[19] ATOMS, MOLECULES, SOLIDS, AND SURFACES - APPLICATIONS OF THE GENERALIZED GRADIENT APPROXIMATION FOR EXCHANGE AND CORRELATION [J].

PERDEW, JP ;

CHEVARY, JA ;

VOSKO, SH ;

JACKSON, KA ;

PEDERSON, MR ;

SINGH, DJ ;

FIOLHAIS, C .

PHYSICAL REVIEW B, 1992, 46 (11) :6671-6687

[20] Characterization of a model Ziegler-Natta catalyst for ethylene polymerization [J].

Schmidt, J ;

Risse, T ;

Hamann, H ;

Freund, HJ .

JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (24) :10861-10868

← 1 2 3 →