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
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
收藏
页码:2635 / 2638
页数:4
相关论文
共 26 条
[1]  
[Anonymous], 2010, ANGEW CHEM-GER EDIT
[2]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[3]   PROJECTOR AUGMENTED-WAVE METHOD [J].
BLOCHL, PE .
PHYSICAL REVIEW B, 1994, 50 (24) :17953-17979
[4]   THEORY OF THE OXIDATION OF METALS [J].
CABRERA, N ;
MOTT, NF .
REPORTS ON PROGRESS IN PHYSICS, 1948, 12 :163-184
[5]   Continuous wave electron paramagnetic resonance investigation of the hyperfine structure of 17O2- adsorbed on the MgO surface [J].
Chiesa, M ;
Giamello, E ;
Paganini, MC ;
Sojka, Z ;
Murphy, DM .
JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (10) :4266-4274
[6]   Intermolecular electron transfer on the surface of MgO nanoparticles [J].
Diwald, O ;
Knözinger, E .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (13) :3495-3502
[7]  
Ertl G., 2008, Handbook of Heterogeneous Catalysis, V1, DOI DOI 10.1002/9783527610044.HETCAT0130
[8]   Adsorption and activation of O2 at Au chains on MgO/Mo thin films [J].
Frondelius, Pentti ;
Hakkinen, Hannu ;
Honkala, Karoliina .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (07) :1483-1492
[9]   Mechanism for NO2 charging on metal supported MgO [J].
Groenbeck, Henrik .
JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (24) :11977-11981
[10]   Low Temperature CO Oxidation over Supported Ultrathin MgO Films [J].
Hellman, Anders ;
Klacar, Simon ;
Groenbeck, Henrik .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (46) :16636-+