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Title: Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study

Abstract

Hydrodechlorination is a promising method for treating toxic chlorocarbon compounds. Pd is among the most effective catalysts for chloroform hydrodechlorination, and experiments have shown that the Pd–Au alloy catalyst yields superior catalytic performance over pure Pd. In this paper, we examine the chloroform hydrodechlorination mechanism over Pd(1 1 1) and Pd ML/Au(1 1 1) surfaces using periodic, self-consistent density functional theory calculations (DFT, GGA–PW91) and maximum rate analysis. We suggest that the reaction occurs on both surfaces through complete dechlorination of chloroform followed by hydrogenation of CH* to methane, and that the initial dechlorination step is likely the rate-limiting step. Finally, on Pd(1 1 1), the chloroform dechlorination barrier is 0.24 eV higher than the desorption barrier, whereas on Pd ML/Au(1 1 1), the chloroform dechlorination barrier is 0.07 eV lower than the desorption barrier, which can explain the higher hydrodechlorination activity of the Pd–Au alloy catalyst.

Authors:
 [1];  [2];  [1];  [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States); Chinese Academy of Sciences (CAS), Beijing (China)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1395857
Alternate Identifier(s):
OSTI ID: 1401431
Grant/Contract Number:  
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231; 21276255
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alloys; carbon; chlorine; density functional calculations; hydrogenation

Citation Formats

Xu, Lang, Yao, Xiaoqian, Khan, Ahmad, and Mavrikakis, Manos. Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study. United States: N. p., 2016. Web. doi:10.1002/cctc.201600144.
Xu, Lang, Yao, Xiaoqian, Khan, Ahmad, & Mavrikakis, Manos. Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study. United States. doi:10.1002/cctc.201600144.
Xu, Lang, Yao, Xiaoqian, Khan, Ahmad, and Mavrikakis, Manos. Wed . "Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study". United States. doi:10.1002/cctc.201600144. https://www.osti.gov/servlets/purl/1395857.
@article{osti_1395857,
title = {Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study},
author = {Xu, Lang and Yao, Xiaoqian and Khan, Ahmad and Mavrikakis, Manos},
abstractNote = {Hydrodechlorination is a promising method for treating toxic chlorocarbon compounds. Pd is among the most effective catalysts for chloroform hydrodechlorination, and experiments have shown that the Pd–Au alloy catalyst yields superior catalytic performance over pure Pd. In this paper, we examine the chloroform hydrodechlorination mechanism over Pd(1 1 1) and PdML/Au(1 1 1) surfaces using periodic, self-consistent density functional theory calculations (DFT, GGA–PW91) and maximum rate analysis. We suggest that the reaction occurs on both surfaces through complete dechlorination of chloroform followed by hydrogenation of CH* to methane, and that the initial dechlorination step is likely the rate-limiting step. Finally, on Pd(1 1 1), the chloroform dechlorination barrier is 0.24 eV higher than the desorption barrier, whereas on PdML/Au(1 1 1), the chloroform dechlorination barrier is 0.07 eV lower than the desorption barrier, which can explain the higher hydrodechlorination activity of the Pd–Au alloy catalyst.},
doi = {10.1002/cctc.201600144},
journal = {ChemCatChem},
number = 9,
volume = 8,
place = {United States},
year = {2016},
month = {4}
}

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Works referenced in this record:

Projector augmented-wave method
journal, December 1994


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992