Chloroform Hydrodechlorination on Palladium Surfaces: A Comparative DFT Study on Pd(111), Pd(100), and Pd(211)

Xu, Lang; Bhandari, Saurabh; Chen, Jiming; Glasgow, Jonathan; Mavrikakis, Manos

doi:10.1007/s11244-019-01218-6

Chloroform Hydrodechlorination on Palladium Surfaces: A Comparative DFT Study on Pd(111), Pd(100), and Pd(211)

Journal Article · Sun Jan 12 23:00:00 EST 2020 · Topics in Catalysis

DOI:https://doi.org/10.1007/s11244-019-01218-6· OSTI ID:1616958

Xu, Lang ^[1]; Bhandari, Saurabh ^[2]; Chen, Jiming ^[2]; Glasgow, Jonathan ^[2]; ^[2]

Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison Department of Chemical and Biological Engineering
Univ. of Wisconsin, Madison, WI (United States)

Palladium has been shown to be an effective catalyst for chloroform hydrodechlorination, which serves as a promising treatment method for industrial chloroform waste. To investigate the structure sensitivity of this chemistry on Pd surfaces, we performed a density functional theory (DFT, GGA-PW91) study of the chloroform hydrodechlorination reaction on three distinct facets: Pd(111), Pd(100), and Pd(211). Based on the DFT results, the binding strengths of most surface intermediates generally increase in the following order: Pd(111) < Pd(100) < Pd(211). On all three Pd facets, methane is formed as the preferred reaction product through a pathway in which CHCl₃* is fully dechlorinated to CH* first, and then hydrogenated to CH₄. We constructed potential energy diagrams (PED) and compared the reaction energetics for chloroform hydrodechlorination on the three Pd facets. We propose that the competition between the desorption of chloroform and its initial dechlorination to form CHCl₂* likely determines the hydrodechlorination activity of the catalyst. On Pd(111), the desorption of chloroform is energetically favored over its dechlorination while the dechlorination barriers are lower than the desorption barriers on Pd(100) and Pd(211). On the other hand, Pd(100) and Pd(211) bind atomic chlorine stronger and also catalyze the formation of atomic carbon effectively; both are potential site-blocking species. Our results suggest that the more open facets and step edge sites of a Pd nanoparticle may carry higher intrinsic activity towards chloroform hydrodechlorination than the close-packed facets, yet these under-coordinated sites are more prone to catalyst poisoning.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Contributing Organization:: National Energy Research Scientific Computing Center (NERSC) and the Center for Nanoscale Materials (CNM) at Argonne National Laboratory (ANL)

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

OSTI ID:: 1616958

Journal Information:: Topics in Catalysis, Journal Name: Topics in Catalysis Vol. 63; ISSN 1022-5528

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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