Nature of the chemical bond between metal atoms and oxide surfaces: New evidences from spin density studies of K atoms on alkaline earth oxides

被引:76
作者
Chiesa, M
Giamello, E
Di Valentin, C
Pacchioni, G
Sojka, Z
Van Doorslaer, S
机构
[1] Univ Turin, Dipartimento Chim IFM, I-10125 Turin, Italy
[2] Univ Turin, NIS Ctr Excellence, I-10125 Turin, Italy
[3] Univ Milano Bicocca, Dipartimento Sci Mat, I-20125 Milan, Italy
[4] Jagiellonian Univ, Dept Chem, PL-30060 Krakow, Poland
[5] Jagiellonian Univ, Reg Lab Physicochem Anal & Struct Res, PL-30060 Krakow, Poland
[6] Univ Instelling Antwerp, Dept Phys, Lab Spect Biophys & Catalysis, B-2610 Antwerp, Belgium
关键词
D O I
10.1021/ja0542901
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We have studied the interaction of K atoms with the surface of polycrystalline alkaline-earth metal oxides (MgO, CaC, SrO) by means of CW- and Pulsed-EPR, UV-Vis-NIR spectroscopies and DFT cluster model calculations. The K adsorption site is proposed to be an anionic reverse corner formed at the intersection of two steps, where K binds by more than 1 eV, resulting in thermally stable species up to about 100 K. The bonding has small covalent and large polarization contributions, and the K atom remains neutral, With one unpaired electron in the valence shell. The interaction results in strong modifications of the K electronic wave function which are directly reflected by the hyperfine coupling constant, (K)a(iso). This is found to be a very efficient "probe" to measure the degree of metal-oxide interaction which directly depends on the Substrate basicity. These results provide an original and general model of the early stages of the metal-support interaction in the case of ionic oxides.
引用
收藏
页码:16935 / 16944
页数:10
相关论文
共 62 条
  • [41] A review of oxygen-17 solid-state NMR of organic materials -: towards biological applications
    Lemaître, V
    Smith, ME
    Watts, A
    [J]. SOLID STATE NUCLEAR MAGNETIC RESONANCE, 2004, 26 (3-4) : 215 - 235
  • [43] Numerical simulation of one- and two-dimensional ESEEM experiments
    Madi, ZL
    Van Doorslaer, S
    Schweiger, A
    [J]. JOURNAL OF MAGNETIC RESONANCE, 2002, 154 (02) : 181 - 191
  • [44] ON MODELING THE INTERACTION OF CO ON THE MGO(100) SURFACE
    MEJIAS, JA
    MARQUEZ, AM
    SANZ, JF
    FERNANDEZGARCIA, M
    RICART, JM
    SOUSA, C
    ILLAS, F
    [J]. SURFACE SCIENCE, 1995, 327 (1-2) : 59 - 73
  • [45] A new model describing the metal-support interaction in noble metal catalysts
    Mojet, BL
    Miller, JT
    Ramaker, DE
    Koningsberger, DC
    [J]. JOURNAL OF CATALYSIS, 1999, 186 (02) : 373 - 386
  • [46] A NOVEL LI IONIC CLUSTER AT THE SURFACE OF MGO
    MURPHY, D
    GIAMELLO, E
    ZECCHINA, A
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (09) : 1739 - 1742
  • [47] A NOVEL TRAPPED ELECTRON CENTER ON SODIUM VAPOR DOPED MAGNESIUM-OXIDE
    MURPHY, D
    GIAMELLO, E
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (33) : 7929 - 7932
  • [48] BONDING BETWEEN CO AND THE MGO(001) SURFACE - A MODIFIED PICTURE
    NYGREN, MA
    PETTERSSON, LGM
    BARANDIARAN, Z
    SEIJO, L
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (03) : 2010 - 2018
  • [49] Pacchioni G, 2003, CATALYSIS AND ELECTROCATALYSIS AT NANOPARTICLE SURFACES, P65
  • [50] AB-INITIO CLUSTER MODEL-CALCULATIONS ON THE CHEMISORPTION OF CO2 AND SO2 PROBE MOLECULES ON MGO AND CAO (100)SURFACES - A THEORETICAL MEASURE OF OXIDE BASICITY
    PACCHIONI, G
    RICART, JM
    ILLAS, F
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) : 10152 - 10158