Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2(110) surface

Yeohoon Yoon, Yang Gang Wang, Roger Rousseau, Vassiliki Alexandra Glezakou

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of the partially reduced TiO2(110) rutile surface to investigate the nature of charge transfer and the role of nonadiabatic effects on three prototypical redox reactions: (i) O2 adsorption, (ii) CO oxidation, and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2 -, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state because of the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (nonadiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a nonadiabatic charge transfer to form an adsorbed CO2 - species, followed by a second nonadiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes.

Original languageEnglish
Pages (from-to)1764-1771
Number of pages8
JournalACS Catalysis
Volume5
Issue number3
DOIs
Publication statusPublished - Mar 6 2015

Fingerprint

Oxides
Charge transfer
Carbon
Carbon Monoxide
Ground state
Density functional theory
Adsorption
Oxidation
Redox reactions
Kinetic parameters
Reaction rates
Oxidation-Reduction
titanium dioxide

Keywords

  • carbon oxides
  • charge transfer
  • Marcus theory
  • nonadiabatic effects
  • redox chemistry
  • rutile TiO

ASJC Scopus subject areas

  • Catalysis

Cite this

Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2(110) surface. / Yoon, Yeohoon; Wang, Yang Gang; Rousseau, Roger; Glezakou, Vassiliki Alexandra.

In: ACS Catalysis, Vol. 5, No. 3, 06.03.2015, p. 1764-1771.

Research output: Contribution to journalArticle

Yoon, Yeohoon ; Wang, Yang Gang ; Rousseau, Roger ; Glezakou, Vassiliki Alexandra. / Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2(110) surface. In: ACS Catalysis. 2015 ; Vol. 5, No. 3. pp. 1764-1771.
@article{e301f9a187de4cb6beb3ad43e515d57b,
title = "Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2(110) surface",
abstract = "We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of the partially reduced TiO2(110) rutile surface to investigate the nature of charge transfer and the role of nonadiabatic effects on three prototypical redox reactions: (i) O2 adsorption, (ii) CO oxidation, and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2 -, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state because of the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (nonadiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a nonadiabatic charge transfer to form an adsorbed CO2 - species, followed by a second nonadiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes.",
keywords = "carbon oxides, charge transfer, Marcus theory, nonadiabatic effects, redox chemistry, rutile TiO",
author = "Yeohoon Yoon and Wang, {Yang Gang} and Roger Rousseau and Glezakou, {Vassiliki Alexandra}",
year = "2015",
month = "3",
day = "6",
doi = "10.1021/cs501873m",
language = "English",
volume = "5",
pages = "1764--1771",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Impact of nonadiabatic charge transfer on the rate of redox chemistry of carbon oxides on rutile TiO2(110) surface

AU - Yoon, Yeohoon

AU - Wang, Yang Gang

AU - Rousseau, Roger

AU - Glezakou, Vassiliki Alexandra

PY - 2015/3/6

Y1 - 2015/3/6

N2 - We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of the partially reduced TiO2(110) rutile surface to investigate the nature of charge transfer and the role of nonadiabatic effects on three prototypical redox reactions: (i) O2 adsorption, (ii) CO oxidation, and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2 -, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state because of the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (nonadiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a nonadiabatic charge transfer to form an adsorbed CO2 - species, followed by a second nonadiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes.

AB - We present the results of a density functional theory (DFT) within the LDA+U approximation on large models of the partially reduced TiO2(110) rutile surface to investigate the nature of charge transfer and the role of nonadiabatic effects on three prototypical redox reactions: (i) O2 adsorption, (ii) CO oxidation, and (iii) CO2 reduction. Charge-constrained DFT (cDFT) is used to estimate kinetic parameters for a Marcus theory rate law that accounts for adiabatic coupling effects on reaction rates. We find that for O2 adsorption, the coupling between adiabatic states is strong, leading to fast charge transfer rates. The lowest energy structures at high coverage consist of two chemisorbed O2 -, one adsorbed at a VO site and the other adsorbed at an adjacent Ti5C site. For CO oxidation, however, all reactions are kinetically hindered on the ground state because of the weak adiabatic coupling at the state crossing, such that one has to overcome two kinetically unfavorable charge transfer events to drive the process (nonadiabatically) on the thermal ground state. The process can be driven by photochemical means but would result in an adsorbed radical [OCOO-] intermediate species. Similarly, CO2 reduction also proceeds via a nonadiabatic charge transfer to form an adsorbed CO2 - species, followed by a second nonadiabatic charge transfer to produce CO. Our analysis provides important computational guidelines for modeling these types of processes.

KW - carbon oxides

KW - charge transfer

KW - Marcus theory

KW - nonadiabatic effects

KW - redox chemistry

KW - rutile TiO

UR - http://www.scopus.com/inward/record.url?scp=84924231376&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84924231376&partnerID=8YFLogxK

U2 - 10.1021/cs501873m

DO - 10.1021/cs501873m

M3 - Article

VL - 5

SP - 1764

EP - 1771

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 3

ER -