Theoretical study of the interaction of molecular oxygen with a reduced TiO2 surface

被引：72

作者：

de Lara-Castells, MP ^{[1
]}

Krause, JL ^{[1
]}

机构：

[1] Univ Florida, Quantum Theory Project, Gainesville, FL 32611 USA

来源：

CHEMICAL PHYSICS LETTERS | 2002年 / 354卷 / 5-6期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/S0009-2614(02)00179-3

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：

We investigate the re-oxidation of the reduced TiO2 (110) surface by adsorption of molecular oxygen using quantum-chemical, ab-initio periodic Hartree-Fock calculations. The absorption sites considered are anion defects and cation Ti(5f) positions. The results show evidence of strong charge transfer from the defect surface to the O-2 molecule. In agreement with experiment, we find that the most stable species is one in which molecular oxygen adsorbs at the defect sites as O-2(-). Adsorption of three O-2 molecules per vacancy site is thermodynamically favored compared to one or two adsorbed molecules. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：483 / 490

页数：8

共 34 条

[1] NON-EMPIRICAL PSEUDOPOTENTIALS FOR MOLECULAR CALCULATIONS .1. PSIBMOL ALGORITHM AND TEST CALCULATIONS [J].

BARTHELAT, JC ;

DURAND, P ;

SERAFINI, A .

MOLECULAR PHYSICS, 1977, 33 (01) :159-180

[2] Cluster and periodic ab-initio calculations on K/TiO2(110) [J].

Bredow, T ;

Aprà, E ;

Catti, M ;

Pacchioni, G .

SURFACE SCIENCE, 1998, 418 (01) :150-165

[3] STRUCTURAL ELECTRONIC RELATIONSHIPS IN INORGANIC SOLIDS - POWDER NEUTRON-DIFFRACTION STUDIES OF THE RUTILE AND ANATASE POLYMORPHS OF TITANIUM-DIOXIDE AT 15 AND 295-K [J].

BURDETT, JK ;

HUGHBANKS, T ;

MILLER, GJ ;

RICHARDSON, JW ;

SMITH, JV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (12) :3639-3646

[4] Relaxation of TiO2(110)-(1x1) using surface X-ray diffraction [J].

Charlton, G ;

Howes, PB ;

Nicklin, CL ;

Steadman, P ;

Taylor, JSG ;

Muryn, CA ;

Harte, SP ;

Mercer, J ;

McGrath, R ;

Norman, D ;

Turner, TS ;

Thornton, G .

PHYSICAL REVIEW LETTERS, 1997, 78 (03) :495-498

[5] Periodic Hartree-Fock study of the adsorption of molecular oxygen on a reduced TiO2 (110) surface [J].

de Lara-Castells, MP ;

Krause, JL .

JOURNAL OF CHEMICAL PHYSICS, 2001, 115 (10) :4798-4810

[6]

DOVESI R, 1998, CRYSTAL 98 USERS MAN

[7] HETEROGENEOUS PHOTOCATALYSIS [J].

FOX, MA ;

DULAY, MT .

CHEMICAL REVIEWS, 1993, 93 (01) :341-357

[8] ELECTROCHEMICAL PHOTOLYSIS OF WATER AT A SEMICONDUCTOR ELECTRODE [J].

FUJISHIMA, A ;

HONDA, K .

NATURE, 1972, 238 (5358) :37-+

[9] TiO2 photocatalysts and diamond electrodes [J].

Fujishima, A ;

Rao, TN ;

Tryk, DA .

ELECTROCHIMICA ACTA, 2000, 45 (28) :4683-4690

[10] The influence of soft vibrational modes on our understanding of oxide surface structure [J].

Harrison, NM ;

Wang, XG ;

Muscat, J ;

Scheffler, M .

FARADAY DISCUSSIONS, 1999, 114 :305-312

← 1 2 3 4 →