Epoxidation of ethylene by silver oxide (Ag2O) cluster: a density functional theory study

Mehmet Ferdi Fellah, Rutger A. van Santen, Isik Onal

Research output: Contribution to journalArticleAcademicpeer-review

10 Citations (Scopus)

Abstract

Density functional theory (DFT) calculations were employed to study epoxidation of ethylene on a [Ag14O9] cluster model representing silver oxide (001) surface. Theoretical results obtained in this study showed that formation paths of acetaldehyde and vinyl alcohol have higher activation barriers than that of ethylene oxide formation path on silver oxide (35 and 35 vs. 20 kcal/mol). Formation of the ethylene oxometallocycle intermediate is found to have a low probability on Ag2O(001) surface. The essential reason for this may be lower basicity of surface oxygen atom on silver oxide surface and the absence of a surface vacancy position to activate ethylene. Adsorbed EO is formed on Ag2O surface cluster without an activation barrier. The activation barriers of the rate-limiting steps for the production of EO mechanisms (via ethyleneoxy and non-activated paths, 20 vs. 14 kcal/mol) are in relatively good agreement with the experimental activation energy values (14, 17 and 22 kcal/mol) reported for EO formation on silver catalyst. Graphical Abstract: [Figure not available: see fulltext.]

Original languageEnglish
Pages (from-to)762-771
Number of pages10
JournalCatalysis Letters
Volume141
Issue number6
DOIs
Publication statusPublished - 1 Jun 2011

Fingerprint

Silver oxides
Epoxidation
Density functional theory
Ethylene
Chemical activation
Ethylene Oxide
Acetaldehyde
Alkalinity
Silver
Vacancies
ethylene
disilver oxide
Alcohols
Activation energy
Oxygen
Atoms
Catalysts
Oxides

Keywords

  • Basicity
  • DFT
  • Epoxidation
  • Ethylene
  • Non-activated path
  • Silver oxide

Cite this

@article{ab4bd66a371247388e0adf5689227fee,
title = "Epoxidation of ethylene by silver oxide (Ag2O) cluster: a density functional theory study",
abstract = "Density functional theory (DFT) calculations were employed to study epoxidation of ethylene on a [Ag14O9] cluster model representing silver oxide (001) surface. Theoretical results obtained in this study showed that formation paths of acetaldehyde and vinyl alcohol have higher activation barriers than that of ethylene oxide formation path on silver oxide (35 and 35 vs. 20 kcal/mol). Formation of the ethylene oxometallocycle intermediate is found to have a low probability on Ag2O(001) surface. The essential reason for this may be lower basicity of surface oxygen atom on silver oxide surface and the absence of a surface vacancy position to activate ethylene. Adsorbed EO is formed on Ag2O surface cluster without an activation barrier. The activation barriers of the rate-limiting steps for the production of EO mechanisms (via ethyleneoxy and non-activated paths, 20 vs. 14 kcal/mol) are in relatively good agreement with the experimental activation energy values (14, 17 and 22 kcal/mol) reported for EO formation on silver catalyst. Graphical Abstract: [Figure not available: see fulltext.]",
keywords = "Basicity, DFT, Epoxidation, Ethylene, Non-activated path, Silver oxide",
author = "Fellah, {Mehmet Ferdi} and {van Santen}, {Rutger A.} and Isik Onal",
year = "2011",
month = "6",
day = "1",
doi = "10.1007/s10562-011-0614-2",
language = "English",
volume = "141",
pages = "762--771",
journal = "Catalysis Letters",
issn = "1011-372X",
publisher = "Springer",
number = "6",

}

Epoxidation of ethylene by silver oxide (Ag2O) cluster : a density functional theory study. / Fellah, Mehmet Ferdi; van Santen, Rutger A.; Onal, Isik.

In: Catalysis Letters, Vol. 141, No. 6, 01.06.2011, p. 762-771.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Epoxidation of ethylene by silver oxide (Ag2O) cluster

T2 - a density functional theory study

AU - Fellah, Mehmet Ferdi

AU - van Santen, Rutger A.

AU - Onal, Isik

PY - 2011/6/1

Y1 - 2011/6/1

N2 - Density functional theory (DFT) calculations were employed to study epoxidation of ethylene on a [Ag14O9] cluster model representing silver oxide (001) surface. Theoretical results obtained in this study showed that formation paths of acetaldehyde and vinyl alcohol have higher activation barriers than that of ethylene oxide formation path on silver oxide (35 and 35 vs. 20 kcal/mol). Formation of the ethylene oxometallocycle intermediate is found to have a low probability on Ag2O(001) surface. The essential reason for this may be lower basicity of surface oxygen atom on silver oxide surface and the absence of a surface vacancy position to activate ethylene. Adsorbed EO is formed on Ag2O surface cluster without an activation barrier. The activation barriers of the rate-limiting steps for the production of EO mechanisms (via ethyleneoxy and non-activated paths, 20 vs. 14 kcal/mol) are in relatively good agreement with the experimental activation energy values (14, 17 and 22 kcal/mol) reported for EO formation on silver catalyst. Graphical Abstract: [Figure not available: see fulltext.]

AB - Density functional theory (DFT) calculations were employed to study epoxidation of ethylene on a [Ag14O9] cluster model representing silver oxide (001) surface. Theoretical results obtained in this study showed that formation paths of acetaldehyde and vinyl alcohol have higher activation barriers than that of ethylene oxide formation path on silver oxide (35 and 35 vs. 20 kcal/mol). Formation of the ethylene oxometallocycle intermediate is found to have a low probability on Ag2O(001) surface. The essential reason for this may be lower basicity of surface oxygen atom on silver oxide surface and the absence of a surface vacancy position to activate ethylene. Adsorbed EO is formed on Ag2O surface cluster without an activation barrier. The activation barriers of the rate-limiting steps for the production of EO mechanisms (via ethyleneoxy and non-activated paths, 20 vs. 14 kcal/mol) are in relatively good agreement with the experimental activation energy values (14, 17 and 22 kcal/mol) reported for EO formation on silver catalyst. Graphical Abstract: [Figure not available: see fulltext.]

KW - Basicity

KW - DFT

KW - Epoxidation

KW - Ethylene

KW - Non-activated path

KW - Silver oxide

UR - http://www.scopus.com/inward/record.url?scp=79958782893&partnerID=8YFLogxK

U2 - 10.1007/s10562-011-0614-2

DO - 10.1007/s10562-011-0614-2

M3 - Article

AN - SCOPUS:79958782893

VL - 141

SP - 762

EP - 771

JO - Catalysis Letters

JF - Catalysis Letters

SN - 1011-372X

IS - 6

ER -