First-principles density functional theory study of sulfur oxide chemistry on transition metal surfaces

In this thesis, the chemistry of sulfur oxides on transition metals is studied extensively via first-principles density functional theory (DFT) computations, focusing on the chemical reactivity and selectivity in sulfur poisoning chemical processes that address environmental concerns. The systematic approach we establish can be extended to general computational studies of small gas-phase molecules interacting with extended surfaces or finite-size clusters. The thesis starts with a theoretical presentation of modem quantum many-body theory that brings together mean-field theory, DFT, and Green's function quantum Monte Carlo theory. The essence of chemical reactivity theory in the framework of DFT is emphasized. The thesis continues with an extensive survey of the current status of sulfur oxide chemistry and an overall presentation of our computational approaches towards a detailed understanding of chemical reactivity and selectivity. The basic guidelines in chemical reactivity are systematically constructed by computed comprehensive thermodynamic data of surface S, O, SO, SO2, SO3, and S04 species as a function of coverage at low and intermediate temperatures. Under these basic guidelines, experimentally measured surface spectra are interpreted, contradictory experimental observations are resolved, and applicable experimental measurements are suggested for confirming computational predictions. Moreover, the chemical reactivity study is supplemented by our chemical kinetics study focusing on the catalytic oxidation of SO2 under oxygen rich conditions. This is the key process that hampers the implementation of the next-generation automotive catalytic converter. The revealed Langmuir-Hinshelwood mechanism demonstrates the essential catalytic performance of the Pt(1 11) surface.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2003

Author dc:creator

• Lin, Xi, 1973-

Advisor dc:contributor.advisor

• Bernhardt L. Trout.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/29642

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/29642