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

Xu, Lang; Yao, Xiaoqian; Khan, Ahmad; Mavrikakis, Manos

doi:10.1002/cctc.201600144

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

Journal Article · Wed Apr 20 00:00:00 EDT 2016 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201600144· OSTI ID:1395857

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)

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. Here 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. 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.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Natural Science Foundation of China (NSFC)

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

OSTI ID:: 1395857

Alternate ID(s):: OSTI ID: 1401431

Journal Information:: ChemCatChem, Vol. 8, Issue 9; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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