An HREELS and TPD study of water on TiO2(110): The extent of molecular versus dissociative adsorption

被引:492
作者
Henderson, MA
机构
[1] Pacific Northwest Natl Lab, Richland, United States
关键词
electron energy loss spectroscopy; low index single crystal surfaces; solid-gas interfaces; surface chemical reaction; thermal desorption; thermal desorption spectroscopy; titanium oxide; vibrations of adsorbed molecules; water;
D O I
10.1016/0039-6028(95)01357-1
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
The interaction of water with the (110) crystal face of TiO2 (rutile) was examined with high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD). Water desorption occurred in three sequential TPD features as a function of exposure at 270, 175 and 155 K, ascribed to monolayer, second layer and multilayer states, respectively. Estimation of the extent to which water molecularly versus dissociatively adsorbed on the TiO2(110) surface was attempted by comparing HREELS and TPD data. Very low water exposures (below 7x10(13) molecules/cm(2)) dissociatively adsorbed at 135 K to surface hydroxyl groups (nu(OH)=3690 cm(-1)), but molecular adsorption (nu(OH)=3420-3505 cm(-1) and delta(HOH)=1625 cm(-1)) resulted from additional water exposure. The appearance of molecular water in HREELS coincided with a red-shift in the O-H stretching frequency of the hydroxyl, presumably due to the formation of hydrogen-bonding interactions with the adsorbed water molecules. Little or no additional water dissociation occurred during heating of the monolayer as inferred from HREELS. Second layer water on TiO2(110) was evident in HREELS by O-H stretching intensity below 3400 cm(-1) indicative of hydrogen-bonding. However, the O-H stretching mode of monolayer water molecules was not red-shifted by the presence of second layer water suggesting that protons on monolayer water molecules were nor involved in hydrogen-bonding second layer water molecules. The influence of second layer water on subsequent layers was evident in both HREELS and TPD.
引用
收藏
页码:151 / 166
页数:16
相关论文
共 49 条
  • [1] BECK DD, 1986, J PHYS CHEM-US, V90, P3122
  • [2] A PROTON MAGNETIC-RESONANCE AND GRAVIMETRIC STUDY OF WATER AND ISOPROPANOL ADSORPTION ON MICROCRYSTALLINE RUTILE .1. ADSORPTION SITES
    BODDENBERG, B
    HORSTMANN, W
    [J]. BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1988, 92 (04): : 519 - 524
  • [3] DESIGN CONSIDERATIONS FOR SIMPLE GAS DOSERS IN SURFACE SCIENCE APPLICATIONS
    CAMPBELL, CT
    VALONE, SM
    [J]. JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A-VACUUM SURFACES AND FILMS, 1985, 3 (02): : 408 - 411
  • [4] HIGH-RESOLUTION ELECTRON-ENERGY-LOSS SPECTROSCOPY OF ISOLATED HYDROXYL-GROUPS ON ALPHA-AL2O3(0001)
    COUSTET, V
    JUPILLE, J
    [J]. SURFACE SCIENCE, 1994, 307 (1 -3 pt B) : 1161 - 1165
  • [5] THE HIGH-RESOLUTION ELECTRON-ENERGY-LOSS SPECTRUM OF TIO2(110)
    COX, PA
    EGDELL, RG
    ERIKSEN, S
    FLAVELL, WR
    [J]. JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 1986, 39 (1-4) : 117 - 126
  • [6] APPLICATION OF FOURIER-TRANSFORM TECHNIQUES TO DECONVOLUTION OF HREEL SPECTRA
    COX, PA
    FLAVELL, WR
    WILLIAMS, AA
    EGDELL, RG
    [J]. SURFACE SCIENCE, 1985, 152 (APR) : 784 - 790
  • [7] THE ADSORPTION AND THERMAL-DECOMPOSITION OF WATER ON CLEAN AND OXYGEN-PREDOSED AL(111)
    CROWELL, JE
    CHEN, JG
    HERCULES, DM
    YATES, JT
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (10) : 5804 - 5815
  • [8] THE ADSORPTION OF WATER ON SRTIO3 AND TIO2 - A REAPPRAISAL
    ERIKSEN, S
    NAYLOR, PD
    EGDELL, RG
    [J]. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 1987, 43 (12): : 1535 - 1538
  • [9] A THEORETICAL INVESTIGATION OF WATER-ADSORPTION ON TITANIUM-DIOXIDE SURFACES
    FAHMI, A
    MINOT, C
    [J]. SURFACE SCIENCE, 1994, 304 (03) : 343 - 359
  • [10] THEORETICAL INVESTIGATION OF HYDROXYLATED OXIDE SURFACES
    GONIAKOWSKI, J
    NOGUERA, C
    [J]. SURFACE SCIENCE, 1995, 330 (03) : 337 - 349