Interactions between hydrogen and tungsten carbide: A first principles study

Yongjie Xi, Liang Huang, Robert C. Forrey, Hansong Cheng

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Tungsten carbide has been proposed to be a potential inexpensive alternative to platinum for catalyzing hydrogenation reactions. Using density functional theory (DFT) calculations, we performed a systematic study on the geometries and electronic structures of small (WC)n(n = 1-10) clusters. A cubic-like growth of WC clusters was found to be the preferred pathway. The interactions between the WC clusters and hydrogen were compared to interactions of hydrogen with the WC(0001) surface. Both atomic clusters and the crystalline surface of WC can lead to facile dissociation of H2while the activation energy on the former is even lower; the H diffusion barrier on WC clusters was found to be significantly higher than that on the WC(0001) surface, yet both of the calculated diffusion barriers are well above the values on the platinum counterpart. The lack of hydrogen mobility may exert a profound influence on the kinetics of hydrogen for participating in reactions on WC. The desorption strength of H on (WC)n(n = 2, 4, 6, 9) at various hydrogen coverages was explored and the hydrogen saturated (WC)9cluster was used to rationalize the catalytic formation of hydrogen tungsten bronzes. The study provides insights which may be useful for efforts to replace Pt with WC in catalytic processes involving hydrogen.

Original languageEnglish (US)
Pages (from-to)39912-39919
Number of pages8
JournalRSC Advances
Volume4
Issue number75
DOIs
StatePublished - 2014

Fingerprint

Tungsten carbide
Hydrogen
Diffusion barriers
Platinum
Tungsten
tungsten carbide
Bronze
Hydrogenation
Electronic structure
Density functional theory
Desorption
Activation energy
Crystalline materials
Kinetics
Geometry

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Xi, Yongjie ; Huang, Liang ; Forrey, Robert C. ; Cheng, Hansong. / Interactions between hydrogen and tungsten carbide : A first principles study. In: RSC Advances. 2014 ; Vol. 4, No. 75. pp. 39912-39919.
@article{60cb8f4c8da341dbb6a98d430ba5934b,
title = "Interactions between hydrogen and tungsten carbide: A first principles study",
abstract = "Tungsten carbide has been proposed to be a potential inexpensive alternative to platinum for catalyzing hydrogenation reactions. Using density functional theory (DFT) calculations, we performed a systematic study on the geometries and electronic structures of small (WC)n(n = 1-10) clusters. A cubic-like growth of WC clusters was found to be the preferred pathway. The interactions between the WC clusters and hydrogen were compared to interactions of hydrogen with the WC(0001) surface. Both atomic clusters and the crystalline surface of WC can lead to facile dissociation of H2while the activation energy on the former is even lower; the H diffusion barrier on WC clusters was found to be significantly higher than that on the WC(0001) surface, yet both of the calculated diffusion barriers are well above the values on the platinum counterpart. The lack of hydrogen mobility may exert a profound influence on the kinetics of hydrogen for participating in reactions on WC. The desorption strength of H on (WC)n(n = 2, 4, 6, 9) at various hydrogen coverages was explored and the hydrogen saturated (WC)9cluster was used to rationalize the catalytic formation of hydrogen tungsten bronzes. The study provides insights which may be useful for efforts to replace Pt with WC in catalytic processes involving hydrogen.",
author = "Yongjie Xi and Liang Huang and Forrey, {Robert C.} and Hansong Cheng",
year = "2014",
doi = "10.1039/c4ra06225f",
language = "English (US)",
volume = "4",
pages = "39912--39919",
journal = "RSC Advances",
issn = "2046-2069",
publisher = "Royal Society of Chemistry",
number = "75",

}

Interactions between hydrogen and tungsten carbide : A first principles study. / Xi, Yongjie; Huang, Liang; Forrey, Robert C.; Cheng, Hansong.

In: RSC Advances, Vol. 4, No. 75, 2014, p. 39912-39919.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Interactions between hydrogen and tungsten carbide

T2 - A first principles study

AU - Xi, Yongjie

AU - Huang, Liang

AU - Forrey, Robert C.

AU - Cheng, Hansong

PY - 2014

Y1 - 2014

N2 - Tungsten carbide has been proposed to be a potential inexpensive alternative to platinum for catalyzing hydrogenation reactions. Using density functional theory (DFT) calculations, we performed a systematic study on the geometries and electronic structures of small (WC)n(n = 1-10) clusters. A cubic-like growth of WC clusters was found to be the preferred pathway. The interactions between the WC clusters and hydrogen were compared to interactions of hydrogen with the WC(0001) surface. Both atomic clusters and the crystalline surface of WC can lead to facile dissociation of H2while the activation energy on the former is even lower; the H diffusion barrier on WC clusters was found to be significantly higher than that on the WC(0001) surface, yet both of the calculated diffusion barriers are well above the values on the platinum counterpart. The lack of hydrogen mobility may exert a profound influence on the kinetics of hydrogen for participating in reactions on WC. The desorption strength of H on (WC)n(n = 2, 4, 6, 9) at various hydrogen coverages was explored and the hydrogen saturated (WC)9cluster was used to rationalize the catalytic formation of hydrogen tungsten bronzes. The study provides insights which may be useful for efforts to replace Pt with WC in catalytic processes involving hydrogen.

AB - Tungsten carbide has been proposed to be a potential inexpensive alternative to platinum for catalyzing hydrogenation reactions. Using density functional theory (DFT) calculations, we performed a systematic study on the geometries and electronic structures of small (WC)n(n = 1-10) clusters. A cubic-like growth of WC clusters was found to be the preferred pathway. The interactions between the WC clusters and hydrogen were compared to interactions of hydrogen with the WC(0001) surface. Both atomic clusters and the crystalline surface of WC can lead to facile dissociation of H2while the activation energy on the former is even lower; the H diffusion barrier on WC clusters was found to be significantly higher than that on the WC(0001) surface, yet both of the calculated diffusion barriers are well above the values on the platinum counterpart. The lack of hydrogen mobility may exert a profound influence on the kinetics of hydrogen for participating in reactions on WC. The desorption strength of H on (WC)n(n = 2, 4, 6, 9) at various hydrogen coverages was explored and the hydrogen saturated (WC)9cluster was used to rationalize the catalytic formation of hydrogen tungsten bronzes. The study provides insights which may be useful for efforts to replace Pt with WC in catalytic processes involving hydrogen.

UR - http://www.scopus.com/inward/record.url?scp=84907150677&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84907150677&partnerID=8YFLogxK

U2 - 10.1039/c4ra06225f

DO - 10.1039/c4ra06225f

M3 - Article

AN - SCOPUS:84907150677

VL - 4

SP - 39912

EP - 39919

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 75

ER -