A theoretical analysis of adsorption and dissociation of CH3OH on the stoichiometric SnO2(110) surface

被引：67

作者：

Calatayud, M ^{[1
]}

Andrés, J ^{[1
]}

Beltrán, A ^{[1
]}

机构：

[1] Univ Jaume 1, Dept Ciencies Expt, E-12080 Castellon de La Plana, Spain

来源：

SURFACE SCIENCE | 1999年 / 430卷 / 1-3期

关键词：

ab initio quantum chemical methods and calculations; alcohols; chemisorption; density functional calculations; tin oxides;

D O I：

10.1016/S0039-6028(99)00507-5

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：

A theoretical analysis based on the Hartree-Fock pseutdopotential method and a density-functional theory calculation using a hybrid combination of general gradient approximation with pseudopotential procedure has been carried out to study the adsorption and dissociation of methanol on the stoichiometric SnO2(110) surface. The dependence of the results upon model system and computing method is discussed. An optimization procedure of adsorbate and substrate atom positions on a six-layer slab model has been selected to characterize the corresponding geometric parameters, adsorption energy and charge-transfer processes related with the molecularly adsorbed CH3OH and dissociative channels to yield methoxy or methyl fragments. In the high-coverage limit (theta = 1), we find that dissociation of the methanol molecule via the heterolylic cleavage of the C-O bond is favoured. At lower coverage (theta = 1/2), this channel and the molecularly adsorbed methanol present similar adsorption energies. (C) 1999 Elsevier Science B.V. All rights reserved.

引用

页码：213 / 222

页数：10

共 48 条

[11]

DOVESI R, 1996, CRYSTAL95 USERS MANU

[12] THEORETICAL METHOD TO DETERMINE ATOMIC PSEUDOPOTENTIALS FOR ELECTRONIC-STRUCTURE CALCULATIONS OF MOLECULES AND SOLIDS [J].

DURAND, P ;

BARTHELAT, JC .

THEORETICA CHIMICA ACTA, 1975, 38 (04) :283-302

[13] A theoretical study of H2S and MeSH adsorption on TiO2 [J].

Fahmi, A ;

Ahdjoudj, J ;

Minot, C .

SURFACE SCIENCE, 1996, 352 :529-533

[14] OXYGEN-VACANCY-CONTROLLED CHEMISTRY ON A METAL-OXIDE SURFACE - METHANOL DISSOCIATION AND OXIDATION ON SNO2(110) [J].

GERCHER, VA ;

COX, DF ;

THEMLIN, JM .

SURFACE SCIENCE, 1994, 306 (03) :279-293

[15] Modelling of oxide surfaces [J].

Gillan, MJ ;

Kantorovich, LN ;

Lindan, PJD .

CURRENT OPINION IN SOLID STATE & MATERIALS SCIENCE, 1996, 1 (06) :820-826

[16]

GILLAN MJ, 1997, J CHEM SOC FARADAY T, V106, P135

[17] SURFACE ATOMIC AND ELECTRONIC-STRUCTURE OF CASSITERITE SNO2 (110) [J].

GODIN, TJ ;

LAFEMINA, JP .

PHYSICAL REVIEW B, 1993, 47 (11) :6518-6523

[18] The adsorption of H2O on TiO2 and SnO2(110) studied by first-principles calculations [J].

Goniakowski, J ;

Gillan, MJ .

SURFACE SCIENCE, 1996, 350 (1-3) :145-158

[19] Influence of gradient corrections on the bulk and surface properties of TiO2 and SnO2 [J].

Goniakowski, J ;

Holender, JM ;

Kantorovich, LN ;

Gillan, MJ ;

White, JA .

PHYSICAL REVIEW B, 1996, 53 (03) :957-960

[20]

GOPEL W, 1991, SENSORS COMPREHENSIV, V2, P29

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