On the mechanism of dehalogenation of methyl halides (Br and Cl) on Ag(111) and Au(111) surfaces: A DFT study

Basil Raju Karimadom; Dan Meyerstein; Amir Mizrahi; Haya Kornweitz

doi:10.1016/j.apsusc.2022.156059

On the mechanism of dehalogenation of methyl halides (Br and Cl) on Ag(111) and Au(111) surfaces: A DFT study

Basil Raju Karimadom
, Dan Meyerstein
, Amir Mizrahi
, Haya Kornweitz

Ariel University
Ben-Gurion University of the Negev
Nuclear Research Center-Negev

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The dehalogenation reaction mechanism of CH₃X (X = Br, Cl) on Ag(111) and Au(111) surfaces is explored computationally. It is found that the CH₃X species are stronger adsorbed on Au(111) surface than on Ag(111) surface due to the increased charge transfer between the adsorbent and the surface. The dehalogenation on Au(111) and Ag(111) surface is slow due to large activation energy barriers. In presence of water, the release of CH₄ is plausible. CH₄ is also released when pre-adsorbed ^⁎H atoms are on the Ag(111) and Au(111) surfaces. The calculations indicate that the presence of co-adsorbents, mainly charged co-adsorbates, affects the reaction kinetics of CH₃X dehalogenation as their adsorption is accompanied by charge transfer, thus altering the electronic charge of the surface. It is proposed that the kinetics of the dehalogenation of CH₃X depends considerably on the charge on the metallic surface. Ag(111) is found to be a more promising catalyst for the dehalogenation of CH₃X than Au(111).

Original language	English
Article number	156059
Journal	Applied Surface Science
Volume	615
DOIs	https://doi.org/10.1016/j.apsusc.2022.156059
State	Published - 1 Apr 2023
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2022

Funding

This study was partially enabled by a grant from the Pazy Foundation. B.R.K is thankful to Ariel University for a Ph.D. fellowship. We acknowledge the Ariel HPC Center at Ariel University for providing computing resources that have contributed to the research results reported in this paper. We acknowledge Vecteezy.com for providing the vector used in the graphical abstract.

Funders
PAZY Foundation
Ariel University

Keywords

DFT
Dehalogenation
Heterogeneous catalysis
Methyl halides
VASP

Access to Document

10.1016/j.apsusc.2022.156059

Cite this

@article{1dd233ad5d0241d69719ecff4fc75338,

title = "On the mechanism of dehalogenation of methyl halides (Br and Cl) on Ag(111) and Au(111) surfaces: A DFT study",

abstract = "The dehalogenation reaction mechanism of CH3X (X = Br, Cl) on Ag(111) and Au(111) surfaces is explored computationally. It is found that the CH3X species are stronger adsorbed on Au(111) surface than on Ag(111) surface due to the increased charge transfer between the adsorbent and the surface. The dehalogenation on Au(111) and Ag(111) surface is slow due to large activation energy barriers. In presence of water, the release of CH4 is plausible. CH4 is also released when pre-adsorbed ⁎H atoms are on the Ag(111) and Au(111) surfaces. The calculations indicate that the presence of co-adsorbents, mainly charged co-adsorbates, affects the reaction kinetics of CH3X dehalogenation as their adsorption is accompanied by charge transfer, thus altering the electronic charge of the surface. It is proposed that the kinetics of the dehalogenation of CH3X depends considerably on the charge on the metallic surface. Ag(111) is found to be a more promising catalyst for the dehalogenation of CH3X than Au(111).",

keywords = "DFT, Dehalogenation, Heterogeneous catalysis, Methyl halides, VASP",

author = "Karimadom, \{Basil Raju\} and Dan Meyerstein and Amir Mizrahi and Haya Kornweitz",

note = "Publisher Copyright: {\textcopyright} 2022",

year = "2023",

month = apr,

day = "1",

doi = "10.1016/j.apsusc.2022.156059",

language = "אנגלית",

volume = "615",

journal = "Applied Surface Science",

issn = "0169-4332",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - On the mechanism of dehalogenation of methyl halides (Br and Cl) on Ag(111) and Au(111) surfaces

T2 - A DFT study

AU - Karimadom, Basil Raju

AU - Meyerstein, Dan

AU - Mizrahi, Amir

AU - Kornweitz, Haya

PY - 2023/4/1

Y1 - 2023/4/1

N2 - The dehalogenation reaction mechanism of CH3X (X = Br, Cl) on Ag(111) and Au(111) surfaces is explored computationally. It is found that the CH3X species are stronger adsorbed on Au(111) surface than on Ag(111) surface due to the increased charge transfer between the adsorbent and the surface. The dehalogenation on Au(111) and Ag(111) surface is slow due to large activation energy barriers. In presence of water, the release of CH4 is plausible. CH4 is also released when pre-adsorbed ⁎H atoms are on the Ag(111) and Au(111) surfaces. The calculations indicate that the presence of co-adsorbents, mainly charged co-adsorbates, affects the reaction kinetics of CH3X dehalogenation as their adsorption is accompanied by charge transfer, thus altering the electronic charge of the surface. It is proposed that the kinetics of the dehalogenation of CH3X depends considerably on the charge on the metallic surface. Ag(111) is found to be a more promising catalyst for the dehalogenation of CH3X than Au(111).

AB - The dehalogenation reaction mechanism of CH3X (X = Br, Cl) on Ag(111) and Au(111) surfaces is explored computationally. It is found that the CH3X species are stronger adsorbed on Au(111) surface than on Ag(111) surface due to the increased charge transfer between the adsorbent and the surface. The dehalogenation on Au(111) and Ag(111) surface is slow due to large activation energy barriers. In presence of water, the release of CH4 is plausible. CH4 is also released when pre-adsorbed ⁎H atoms are on the Ag(111) and Au(111) surfaces. The calculations indicate that the presence of co-adsorbents, mainly charged co-adsorbates, affects the reaction kinetics of CH3X dehalogenation as their adsorption is accompanied by charge transfer, thus altering the electronic charge of the surface. It is proposed that the kinetics of the dehalogenation of CH3X depends considerably on the charge on the metallic surface. Ag(111) is found to be a more promising catalyst for the dehalogenation of CH3X than Au(111).

KW - DFT

KW - Dehalogenation

KW - Heterogeneous catalysis

KW - Methyl halides

KW - VASP

UR - https://www.scopus.com/pages/publications/85145778181

U2 - 10.1016/j.apsusc.2022.156059

DO - 10.1016/j.apsusc.2022.156059

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

AN - SCOPUS:85145778181

SN - 0169-4332

VL - 615

JO - Applied Surface Science

JF - Applied Surface Science

M1 - 156059

ER -

On the mechanism of dehalogenation of methyl halides (Br and Cl) on Ag(111) and Au(111) surfaces: A DFT study

Abstract

Bibliographical note

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this