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甲醇、甲酸和甲醛在多晶钛和TiO2(100)表面吸附的ESCA研究

ESCA Studies of the Adsorptions of CH3OH, HCOOH and HCHO on Polycrystalline Ti and Tio2(100) Surfaces

  • 摘要: 清洁的多晶金属钛表面碱性强,甲醇、甲酸和甲醛在该表面上均呈分解吸附,表面产生碳化钛、氧化钛、OH、CHx、和CHxO(x ≤ 3)等物种,在甲酸吸附时还可观察到HCOO的存在.TiO2(100)完整表面碱性较弱,在甲醇的吸附反应中,表面只观察到OH、CHx和CHxO,甲醛室温在该表面吸附也产生类似物种,加热至700K,表面形成了HCOO.在TiO2(100)氧缺位表面,室温时甲醇和甲醛的吸附量大于其完整表面,这表明氧缺位表面有较强的碱性,甲醛在其表面吸附并加热至700K,表面并没有HCOO产生;甲酸在其表面吸附,主要产物为CHxO,HCOO浓度十分低.可见TiO2(100)氧缺位表面具有切断C-O键的能力,而TiO2(100)完整表面则具有将HCO氧化为HCOO的能力.

     

    Abstract: The Surfaces of polycrystalline titanlum and TiO2 (100) were characterised by XPS and UPS. For clean polycrystalline titanium surfaces, the Ti(2p) peaks appeared at 453.7eV and 460.8eV binding energies, corresponding to the 3/2 and 1/2 signals. The HeⅠ or HeⅡ induced Ti (3d) band appeared at 0.8eV below the Fermi level. For order TiO2(100) surfaces, the Ti(2p) peaks were at 458.6eV and 464.4eV with no band at 0.8eV observeable in the UPS spectra. Ar+ bombardment would caule defects on the surfaces. Ti(2p) peaks corresponding to the formation of Te2+ and Te3+ were observed. The existance of the 0.8eV band below the Fermi level in the UPS spectra also showed that the surfaces were reduced. O2+ bombardment and annealing at 700K would re-oxidised the defect surface to Tio2(100).
    Metallic titanium is a strong Lewis base. On polycrystalline Ti surfaces, CH3OH, HCOOH and HCHO adsorbed dissociatively at 295K to give surface carbide, oxide, OH, CHx and CHxO (x<3). In the case of HCOOH adsorption, surface formate was formed as well. Order TiO2(100) surfaces are of mild bascity. CH3OH adsorption only gave surfaces OH, CHx and CHxO. Adsorption of HCHO at 295K gave similar species but at 700K, formate was obsenved. On defect TiO2(100) surfaces, oxygen vacancies faciliated C-O bond eleavage. HCOOH adsorbed mainly as HCO and the adsorption of HCHO did not form formate at 700K.

     

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