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Title: A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination

Abstract

Atomic chlorine is known to interact strongly with most late transition metal surfaces. This work aims to identify the relevant chlorine coverage under typical 1,2-dichloroethane hydrodechlorination conditions (T = 423–523 K, PHCl = 10-2–101 bar) and its impact on the reaction energetics. Density functional theory calculations (GGA-PW91) were performed to study the adsorption of chlorine up to 1 monolayer over the close-packed facets of 10 late transition metals (Pt, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Au). The ab initio phase diagram of each chlorine/metal system was constructed. The phase diagrams predicted approximately 1/3 ML chlorine coverage on all metals other than Ag and Au, which remain clean surfaces under hydrodechlorination conditions. The presence of surface chlorine was also found to significantly destabilize the adsorption of reaction intermediates, thus shifting the reaction potential energy diagram upwards. Our results emphasize the importance of explicitly including adsorbed chlorine spectators in properly modeling the catalytic surfaces for the 1,2-dichloroethane hydrodechlorination reaction.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Department of Chemical and Biological Engineering; University of Wisconsin-Madison; Madison; USA
  2. Core Research and Development; The Dow Chemical Company; Midland; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492850
DOE Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Xu, Lang, Stangland, Eric E., and Mavrikakis, Manos. A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination. United States: N. p., 2018. Web. doi:10.1039/c7cy02647a.
Xu, Lang, Stangland, Eric E., & Mavrikakis, Manos. A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination. United States. doi:10.1039/c7cy02647a.
Xu, Lang, Stangland, Eric E., and Mavrikakis, Manos. Mon . "A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination". United States. doi:10.1039/c7cy02647a.
@article{osti_1492850,
title = {A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination},
author = {Xu, Lang and Stangland, Eric E. and Mavrikakis, Manos},
abstractNote = {Atomic chlorine is known to interact strongly with most late transition metal surfaces. This work aims to identify the relevant chlorine coverage under typical 1,2-dichloroethane hydrodechlorination conditions (T = 423–523 K, PHCl = 10-2–101 bar) and its impact on the reaction energetics. Density functional theory calculations (GGA-PW91) were performed to study the adsorption of chlorine up to 1 monolayer over the close-packed facets of 10 late transition metals (Pt, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Au). The ab initio phase diagram of each chlorine/metal system was constructed. The phase diagrams predicted approximately 1/3 ML chlorine coverage on all metals other than Ag and Au, which remain clean surfaces under hydrodechlorination conditions. The presence of surface chlorine was also found to significantly destabilize the adsorption of reaction intermediates, thus shifting the reaction potential energy diagram upwards. Our results emphasize the importance of explicitly including adsorbed chlorine spectators in properly modeling the catalytic surfaces for the 1,2-dichloroethane hydrodechlorination reaction.},
doi = {10.1039/c7cy02647a},
journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 6,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

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