Thickness-Dependent Hydroxylation of MgO(001) Thin Films

被引：54
作者：
Carrasco, Esther [1 ]
Brown, Matthew A. [1 ]
Sterrer, Martin [1 ]
Freund, Hans-Joachim [1 ]
Kwapien, Karolina [2 ]
Sierka, Marek [2 ]
Sauer, Joachim [2 ]
机构：
[1] Fritz Haber Inst Max Planck Gesellschaft, Dept Chem Phys, D-14195 Berlin, Germany
[2] Humboldt Univ, Dept Chem, D-10099 Berlin, Germany
来源：
JOURNAL OF PHYSICAL CHEMISTRY C | 2010年 / 114卷 / 42期
关键词：
DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; AUGMENTED-WAVE METHOD; WATER DISSOCIATION; AB-INITIO; ELECTRONIC-STRUCTURE; AMBIENT CONDITIONS; MGO(100) SURFACES; AQUEOUS-SOLUTIONS; MGO SURFACE;
D O I：
10.1021/jp105294e
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：
Hydroxylation of MgO surfaces has been studied from UHV to mbar pressure for MgO(001) films of different thickness grown on Ag(001) by X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, and density functional theory calculations. In agreement with earlier studies on MgO(001) single crystals, a threshold water pressure on the order of 10(-4) mbar is found for extensive hydroxylation of thick, bulklike MgO films. Decreasing the MgO film thickness shifts the threshold pressure to lower values, being 10(-6) mbar in the limit of 2 monolayer MgO(001)/Ag(001). This result is explained on the basis of the precursor state of periclase MgO(001) dissolution involving hydrolysis of Mg-O surface bonds. The enhanced structural flexibility (polaronic distortion) of the ultrathin MgO film facilitates surface hydroxylation by lowering the barrier for hydrolysis.
引用
收藏
页码：18207 / 18214
页数：8
相关论文
共 57 条
  • [1] Hydrolysis at MgO(100)/Ag(100) oxide-metal interfaces studied by O 1s x-ray photoelectron and MgKL23L23 Auger spectroscopy
    Altieri, S.
    Contri, S. F.
    Valeri, S.
    [J]. PHYSICAL REVIEW B, 2007, 76 (20):
  • [2] Electronic structure and chemical reactivity of oxide-metal interfaces: MgO(100)/Ag(100)
    Altieri, S
    Tjeng, LH
    Sawatzky, GA
    [J]. PHYSICAL REVIEW B, 2000, 61 (24) : 16948 - 16955
  • [3] PROJECTOR AUGMENTED-WAVE METHOD
    BLOCHL, PE
    [J]. PHYSICAL REVIEW B, 1994, 50 (24): : 17953 - 17979
  • [4] Metal oxide surfaces and their interactions with aqueous solutions and microbial organisms
    Brown, GE
    Henrich, VE
    Casey, WH
    Clark, DL
    Eggleston, C
    Felmy, A
    Goodman, DW
    Grätzel, M
    Maciel, G
    McCarthy, MI
    Nealson, KH
    Sverjensky, DA
    Toney, MF
    Zachara, JM
    [J]. CHEMICAL REVIEWS, 1999, 99 (01) : 77 - 174
  • [5] Enhanced Stability of Gold Clusters Supported on Hydroxylated MgO(001) Surfaces
    Brown, Matthew A.
    Carrasco, Esther
    Sterrer, Martin
    Freund, Hans-Joachim
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (12) : 4064 - +
  • [6] THEORY OF THE OXIDATION OF METALS
    CABRERA, N
    MOTT, NF
    [J]. REPORTS ON PROGRESS IN PHYSICS, 1948, 12 : 163 - 184
  • [7] Dynamic ion pairs in the adsorption of isolated water molecules on alkaline-earth oxide (001) surfaces
    Carrasco, Javier
    Illas, Francesc
    Lopez, Nuria
    [J]. PHYSICAL REVIEW LETTERS, 2008, 100 (01)
  • [8] Infrared characterization of hydroxyl groups on MgO: A periodic and cluster density functional theory study
    Chizallet, Celine
    Costentin, Guylene
    Che, Michel
    Delbecq, Francoise
    Sautet, Philippe
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (20) : 6442 - 6452
  • [9] Chizallet C, 2006, J PHYS CHEM B, V110, P15878, DOI [10.1021/jp060840l, 10.1021/jp0608401]
  • [10] THE HYDROXYLATED SURFACE OF MGO POWDERS AND THE FORMATION OF SURFACE SITES
    COLUCCIA, S
    LAVAGNINO, S
    MARCHESE, L
    [J]. MATERIALS CHEMISTRY AND PHYSICS, 1988, 18 (5-6) : 445 - 464
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