Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

Shenoy, Chaitra S.; Khan, Tuhin S.; Verma, Kirti; Tsige, Mesfin; Jha, Kshitij C.; Haider, M. Ali; Gupta, Shelaka

doi:10.1039/d1re00252j

Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

Journal Article · Fri Sep 17 00:00:00 EDT 2021 · Reaction Chemistry & Engineering

DOI:https://doi.org/10.1039/d1re00252j· OSTI ID:1978821

Shenoy, Chaitra S. ^[1]; Khan, Tuhin S. ^[2]; Verma, Kirti ^[3]; ^[4]; ^[5]; ^[3]; ^[6]

Indian Institute of Technology Delhi (India); OSTI
CSIR – Indian Institute of Petroleum, Dehradun (India)
Indian Institute of Technology Delhi (India)
University of Akron, OH (United States)
University of Akron, OH (United States); Biena Tech LLC, Akron, OH (United States); Indian Institute of Technology Delhi (India)
Indian Institute of Technology Hyderabad, Telangana (India)

Periodic density functional theory (DFT) calculations are employed to understand the origin of structure sensitivity in hydrodechlorination (HDC) of trichloroethylene (TCE) over different facets of a palladium catalyst. The HDC reaction is simulated on the terrace (Pd (111) and Pd (100)) and undercoordinated (Pd (211) and Pd (110)) sites of the Pd catalyst. The most stable binding configuration of TCE on the Pd surfaces is observed to be through the di-σ mode of binding, wherein each carbon atom of the TCE molecule is adsorbed atop of the Pd atom. On comparing TCE adsorption over different facets of Pd, a maximum binding energy of –178 kJ mol^–1 is calculated over the Pd (110) surface. TCE, upon adsorption on Pd catalyst, undergoes dechlorination followed by hydrogenation of the hydrocarbon intermediates. The activation energies for C–Cl bond dissociation steps are significantly low when compared to the hydrogenation steps. The chlorine released from dechlorination tends to block the active sites, thereby poisoning the surface with high binding energies (B.E > –160 kJ mol^–1) on all the surfaces. The trend in chlorine binding energies on Pd facets follows: Pd (110) > Pd (211) > Pd (100) > Pd (111). The removal of surface chlorine is facilitated by its reaction with surface hydrogen to form hydrogen chloride. The activation energy for hydrogen chloride formation is calculated to be 90 kJ mol^–1 and 88 kJ mol^–1 on Pd (111) and Pd (100) terrace sites, respectively and 109 kJ mol^–1 and 118 kJ mol^–1 on the step Pd (211) and corrugated Pd (110) facets, respectively. This suggests the ease of removal of Cl as HCl from the terrace sites as compared to the step and corrugated sites. The structure sensitivity in the TCE HDC reaction could possibly arise due to the differences in the energetics of Cl removal on different Pd facets. As a result, this mechanistic understanding could provide a rationale for designing suitable catalysts for the HDC of TCE.

View Accepted Manuscript (DOE)

Research Organization:: Biena Tech, LLC, Akron, OH (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0018875

OSTI ID:: 1978821

Alternate ID(s):: OSTI ID: 1820667

Journal Information:: Reaction Chemistry & Engineering, Journal Name: Reaction Chemistry & Engineering Journal Issue: 12 Vol. 6; ISSN RCEEBW; ISSN 2058-9883

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

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