A first-principles analysis for sulfur tolerance of CeO 2 in solid oxide fuel cells

Hsin Tsung Chen; YongMan Choi; Meilin Liu; Ming-Chang Lin

doi:10.1021/jp0705774

A first-principles analysis for sulfur tolerance of CeO ₂ in solid oxide fuel cells

Hsin Tsung Chen, YongMan Choi^*, Meilin Liu, Ming-Chang Lin

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

64 Scopus citations

Abstract

The mechanism for H ₂S-CeO ₂(111) interactions in solid oxide fuel cells (SOFCs) has been investigated by using periodic density functional theory (DFT) calculations. In order to properly characterize the effect of the localization of Ce _4f states on the interactions, DFT + U calculations were applied. Adsorption of H2S, SH, and atomic S was initially examined to locate energetically favorable intermediates. The species adsorb favorably at the Ce-top, O-top, and Ce-O bridging sites, respectively. Potential energy profiles for the H ₂SCeO ₂ (111) interactions along the three product channels producing H ₂, H ₂O, and SO ₂ were constructed using the nudged elastic band (NEB) method. Calculations show that H ₂S weakly bounds on CeO ₂(111) with a small binding energy, followed by dehydrogenation processes, forming surface sulfur species with an exothermicity of 29.9 kcal/mol. Molecular-level calculations demonstrated that the SO ₂-forming pathway is energetically most favorable.

Original language	English
Pages (from-to)	11117-11122
Number of pages	6
Journal	Journal of Physical Chemistry C
Volume	111
Issue number	29
DOIs	https://doi.org/10.1021/jp0705774
State	Published - 26 Jul 2007

Keywords

DENSITY-FUNCTIONAL THEORY
GENERALIZED GRADIENT APPROXIMATION
LOW-INDEX SURFACES
ELECTRONIC-STRUCTURE
MESOPOROUS CERIA
HYDROGEN-SULFIDE
ANODES
TEMPERATURE
REDUCTION
STABILITY

Access to Document

10.1021/jp0705774

Cite this

@article{c46de67230d148118e062cef2a2399b3,

title = "A first-principles analysis for sulfur tolerance of CeO 2 in solid oxide fuel cells",

abstract = "The mechanism for H 2S-CeO 2(111) interactions in solid oxide fuel cells (SOFCs) has been investigated by using periodic density functional theory (DFT) calculations. In order to properly characterize the effect of the localization of Ce 4f states on the interactions, DFT + U calculations were applied. Adsorption of H2S, SH, and atomic S was initially examined to locate energetically favorable intermediates. The species adsorb favorably at the Ce-top, O-top, and Ce-O bridging sites, respectively. Potential energy profiles for the H 2SCeO 2 (111) interactions along the three product channels producing H 2, H 2O, and SO 2 were constructed using the nudged elastic band (NEB) method. Calculations show that H 2S weakly bounds on CeO 2(111) with a small binding energy, followed by dehydrogenation processes, forming surface sulfur species with an exothermicity of 29.9 kcal/mol. Molecular-level calculations demonstrated that the SO 2-forming pathway is energetically most favorable.",

keywords = "DENSITY-FUNCTIONAL THEORY, GENERALIZED GRADIENT APPROXIMATION, LOW-INDEX SURFACES, ELECTRONIC-STRUCTURE, MESOPOROUS CERIA, HYDROGEN-SULFIDE, ANODES, TEMPERATURE, REDUCTION, STABILITY",

author = "Chen, {Hsin Tsung} and YongMan Choi and Meilin Liu and Ming-Chang Lin",

year = "2007",

month = jul,

day = "26",

doi = "10.1021/jp0705774",

language = "English",

volume = "111",

pages = "11117--11122",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "29",

}

TY - JOUR

T1 - A first-principles analysis for sulfur tolerance of CeO 2 in solid oxide fuel cells

AU - Chen, Hsin Tsung

AU - Choi, YongMan

AU - Liu, Meilin

AU - Lin, Ming-Chang

PY - 2007/7/26

Y1 - 2007/7/26

N2 - The mechanism for H 2S-CeO 2(111) interactions in solid oxide fuel cells (SOFCs) has been investigated by using periodic density functional theory (DFT) calculations. In order to properly characterize the effect of the localization of Ce 4f states on the interactions, DFT + U calculations were applied. Adsorption of H2S, SH, and atomic S was initially examined to locate energetically favorable intermediates. The species adsorb favorably at the Ce-top, O-top, and Ce-O bridging sites, respectively. Potential energy profiles for the H 2SCeO 2 (111) interactions along the three product channels producing H 2, H 2O, and SO 2 were constructed using the nudged elastic band (NEB) method. Calculations show that H 2S weakly bounds on CeO 2(111) with a small binding energy, followed by dehydrogenation processes, forming surface sulfur species with an exothermicity of 29.9 kcal/mol. Molecular-level calculations demonstrated that the SO 2-forming pathway is energetically most favorable.

AB - The mechanism for H 2S-CeO 2(111) interactions in solid oxide fuel cells (SOFCs) has been investigated by using periodic density functional theory (DFT) calculations. In order to properly characterize the effect of the localization of Ce 4f states on the interactions, DFT + U calculations were applied. Adsorption of H2S, SH, and atomic S was initially examined to locate energetically favorable intermediates. The species adsorb favorably at the Ce-top, O-top, and Ce-O bridging sites, respectively. Potential energy profiles for the H 2SCeO 2 (111) interactions along the three product channels producing H 2, H 2O, and SO 2 were constructed using the nudged elastic band (NEB) method. Calculations show that H 2S weakly bounds on CeO 2(111) with a small binding energy, followed by dehydrogenation processes, forming surface sulfur species with an exothermicity of 29.9 kcal/mol. Molecular-level calculations demonstrated that the SO 2-forming pathway is energetically most favorable.

KW - DENSITY-FUNCTIONAL THEORY

KW - GENERALIZED GRADIENT APPROXIMATION

KW - LOW-INDEX SURFACES

KW - ELECTRONIC-STRUCTURE

KW - MESOPOROUS CERIA

KW - HYDROGEN-SULFIDE

KW - ANODES

KW - TEMPERATURE

KW - REDUCTION

KW - STABILITY

UR - http://www.scopus.com/inward/record.url?scp=34547693143&partnerID=8YFLogxK

U2 - 10.1021/jp0705774

DO - 10.1021/jp0705774

M3 - Article

AN - SCOPUS:34547693143

SN - 1932-7447

VL - 111

SP - 11117

EP - 11122

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 29

ER -

A first-principles analysis for sulfur tolerance of CeO ₂ in solid oxide fuel cells

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this