Mechanism of hydrodeoxygenation (HDO) in anisole decomposition over metal loaded Brønsted acid sites: Density Functional Theory (DFT) study

Jiajun Zhang, Beatriz Fidalgo, Dekui Shen, Xiaolei Zhang, Sai Gu

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

In this work, the mechanism and intrinsic reaction energy barriers of hydro-deoxygenation (HDO) of anisole, as key stage of the catalytic decomposition over metal-loaded acid support catalysts (bi-functional catalysts), were investigated by Density Functional Theory (DFT). Common transition metals were compared in terms of their adsorption energy when adsorbing anisole molecule for the selection of loading metals. The roles of metal and acid sites in the HDO of phenolic compounds (Phs) over bi-functional catalyst were investigated, and a novel HDO mechanism was proposed by combining Fukui index and bond orders of phenol molecule analyses. HDO reactions of Phs over sole acid sites and the bi-functional catalysts were modelled. The modelling results revealed that, for anisole adsorption, Co, Mo, Ni and Cu showed higher adsorption energy than other transition metals. Molecule analysis results showed that HDO over bi-functional catalysts was dominated by the protonation of the hydroxyl group on Phs. Reaction modelling exhibited that active metals had significant effects in lowering energy barriers of the reactions for all the Phs; the metal active sites facilitated the protonation by developing strong interaction with the adsorbed reactant, and they also aid the hydrogen molecule dissociation. Ni and Mo showed the best catalytic effect on the HDO for most Phs. The effect of side chain methyl substitutes on the HDO reactions for various Phs intermediates during anisole decomposition was also investigated by reaction modelling. Modelling results in this study were found in good agreement with experimental data
LanguageEnglish
Pages30-37
Number of pages8
JournalMolecular Catalysis
Volume454
Early online date21 May 2018
DOIs
Publication statusPublished - 31 Jul 2018

Fingerprint

Density functional theory
Metals
Decomposition
Acids
Catalysts
Molecules
Protonation
Energy barriers
Adsorption
Transition metals
Phenol
Catalyst supports
Hydroxyl Radical
Hydrogen
anisole

Keywords

  • anisole
  • catalytic decomposition
  • hydrodeoxygenation
  • DFT modelling
  • bi-functional catalyst

Cite this

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title = "Mechanism of hydrodeoxygenation (HDO) in anisole decomposition over metal loaded Br{\o}nsted acid sites: Density Functional Theory (DFT) study",
abstract = "In this work, the mechanism and intrinsic reaction energy barriers of hydro-deoxygenation (HDO) of anisole, as key stage of the catalytic decomposition over metal-loaded acid support catalysts (bi-functional catalysts), were investigated by Density Functional Theory (DFT). Common transition metals were compared in terms of their adsorption energy when adsorbing anisole molecule for the selection of loading metals. The roles of metal and acid sites in the HDO of phenolic compounds (Phs) over bi-functional catalyst were investigated, and a novel HDO mechanism was proposed by combining Fukui index and bond orders of phenol molecule analyses. HDO reactions of Phs over sole acid sites and the bi-functional catalysts were modelled. The modelling results revealed that, for anisole adsorption, Co, Mo, Ni and Cu showed higher adsorption energy than other transition metals. Molecule analysis results showed that HDO over bi-functional catalysts was dominated by the protonation of the hydroxyl group on Phs. Reaction modelling exhibited that active metals had significant effects in lowering energy barriers of the reactions for all the Phs; the metal active sites facilitated the protonation by developing strong interaction with the adsorbed reactant, and they also aid the hydrogen molecule dissociation. Ni and Mo showed the best catalytic effect on the HDO for most Phs. The effect of side chain methyl substitutes on the HDO reactions for various Phs intermediates during anisole decomposition was also investigated by reaction modelling. Modelling results in this study were found in good agreement with experimental data",
keywords = "anisole, catalytic decomposition, hydrodeoxygenation, DFT modelling, bi-functional catalyst",
author = "Jiajun Zhang and Beatriz Fidalgo and Dekui Shen and Xiaolei Zhang and Sai Gu",
year = "2018",
month = "7",
day = "31",
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language = "English",
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Mechanism of hydrodeoxygenation (HDO) in anisole decomposition over metal loaded Brønsted acid sites : Density Functional Theory (DFT) study. / Zhang, Jiajun; Fidalgo, Beatriz; Shen, Dekui; Zhang, Xiaolei; Gu, Sai.

Vol. 454, 31.07.2018, p. 30-37.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Mechanism of hydrodeoxygenation (HDO) in anisole decomposition over metal loaded Brønsted acid sites

T2 - Density Functional Theory (DFT) study

AU - Zhang, Jiajun

AU - Fidalgo, Beatriz

AU - Shen, Dekui

AU - Zhang, Xiaolei

AU - Gu, Sai

PY - 2018/7/31

Y1 - 2018/7/31

N2 - In this work, the mechanism and intrinsic reaction energy barriers of hydro-deoxygenation (HDO) of anisole, as key stage of the catalytic decomposition over metal-loaded acid support catalysts (bi-functional catalysts), were investigated by Density Functional Theory (DFT). Common transition metals were compared in terms of their adsorption energy when adsorbing anisole molecule for the selection of loading metals. The roles of metal and acid sites in the HDO of phenolic compounds (Phs) over bi-functional catalyst were investigated, and a novel HDO mechanism was proposed by combining Fukui index and bond orders of phenol molecule analyses. HDO reactions of Phs over sole acid sites and the bi-functional catalysts were modelled. The modelling results revealed that, for anisole adsorption, Co, Mo, Ni and Cu showed higher adsorption energy than other transition metals. Molecule analysis results showed that HDO over bi-functional catalysts was dominated by the protonation of the hydroxyl group on Phs. Reaction modelling exhibited that active metals had significant effects in lowering energy barriers of the reactions for all the Phs; the metal active sites facilitated the protonation by developing strong interaction with the adsorbed reactant, and they also aid the hydrogen molecule dissociation. Ni and Mo showed the best catalytic effect on the HDO for most Phs. The effect of side chain methyl substitutes on the HDO reactions for various Phs intermediates during anisole decomposition was also investigated by reaction modelling. Modelling results in this study were found in good agreement with experimental data

AB - In this work, the mechanism and intrinsic reaction energy barriers of hydro-deoxygenation (HDO) of anisole, as key stage of the catalytic decomposition over metal-loaded acid support catalysts (bi-functional catalysts), were investigated by Density Functional Theory (DFT). Common transition metals were compared in terms of their adsorption energy when adsorbing anisole molecule for the selection of loading metals. The roles of metal and acid sites in the HDO of phenolic compounds (Phs) over bi-functional catalyst were investigated, and a novel HDO mechanism was proposed by combining Fukui index and bond orders of phenol molecule analyses. HDO reactions of Phs over sole acid sites and the bi-functional catalysts were modelled. The modelling results revealed that, for anisole adsorption, Co, Mo, Ni and Cu showed higher adsorption energy than other transition metals. Molecule analysis results showed that HDO over bi-functional catalysts was dominated by the protonation of the hydroxyl group on Phs. Reaction modelling exhibited that active metals had significant effects in lowering energy barriers of the reactions for all the Phs; the metal active sites facilitated the protonation by developing strong interaction with the adsorbed reactant, and they also aid the hydrogen molecule dissociation. Ni and Mo showed the best catalytic effect on the HDO for most Phs. The effect of side chain methyl substitutes on the HDO reactions for various Phs intermediates during anisole decomposition was also investigated by reaction modelling. Modelling results in this study were found in good agreement with experimental data

KW - anisole

KW - catalytic decomposition

KW - hydrodeoxygenation

KW - DFT modelling

KW - bi-functional catalyst

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DO - 10.1016/j.mcat.2018.05.015

M3 - Article

VL - 454

SP - 30

EP - 37

ER -