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

doi:10.1002/cctc.201600144

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

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:

Xu, Lang ^[1] ; Yao, Xiaoqian ^[2] ; Khan, Ahmad ^[1] ; Mavrikakis, Manos ^[1]

Univ. of Wisconsin, Madison, WI (United States)
Chinese Academy of Sciences (CAS), Beijing (China)

Publication Date:: 2016-04-20

Grant/Contract Number:: FG02-05ER15731; AC02-06CH11357; AC02-05CH11231; 21276255

Type:: Accepted Manuscript

Journal Name:: ChemCatChem

Additional Journal Information:: Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 1867-3880

Publisher:: ChemPubSoc Europe

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)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alloys; carbon; chlorine; density functional calculations; hydrogenation

OSTI Identifier:: 1395857

Alternate Identifier(s):: OSTI ID: 1401431


                    Xu, Lang, Yao, Xiaoqian, Khan, Ahmad, and Mavrikakis, Manos. Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First-Principles DFT Study.  United States: N. p.,  
        Web.  doi:10.1002/cctc.201600144.

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                    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.

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                    Xu, Lang, Yao, Xiaoqian, Khan, Ahmad, and Mavrikakis, Manos. 2016.  
        "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.

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

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