DFT study of bio-oil decomposition mechanism on a Co stepped surface: Acetic acid as a model compound

被引：52

作者：

Li, Xinbao ^{[1
]}

Wang, Shurong ^{[2
]}

Zhu, Yingying ^{[1
]}

Yang, Guohua ^{[1
]}

Zheng, Pengjun ^{[1
,3
]}

机构：

[1] Ningbo Univ, Fac Maritime & Transportat, Ningbo 315211, Zhejiang, Peoples R China

[2] Zhejiang Univ, State Key Lab Clean Energy Utilizat, Hangzhou 310027, Zhejiang, Peoples R China

[3] Ningbo Univ Subctr, Natl Traff Management Engn & Technol Res Ctr, Ningbo 315211, Zhejiang, Peoples R China

来源：

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY | 2015年 / 40卷 / 01期

基金：

中国国家自然科学基金;

关键词：

DFT; Bio-oil; Acetic acid; Cobalt; Mechanism; Stepped surface; TOTAL-ENERGY CALCULATIONS; HYDROGEN-PRODUCTION; FAST PYROLYSIS; REACTION PATHWAYS; PROPANOIC ACID; STEAM; ETHANOL; PD(111); CATALYSTS; KINETICS;

D O I：

10.1016/j.ijhydene.2014.11.004

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

To elucidate bio-oil catalytic reforming mechanisms, acetic acid has been selected as a model compound to carry out density functional theory calculations on its decomposition pathways over an active Co stepped surface. The adsorption energies and stable geometries of the reactant and important reaction intermediates have been obtained. Preferential adsorption on a step as opposed to a flat surface has been discerned. The activation barriers and reaction enthalpies for various elementary reactions involved in acetic acid decomposition have also been obtained. Four likely parallel decomposition pathways with activation barriers of less than 0.9 eV have been identified. The most kinetically favorable decomposition pathway is CH3COOH -> CH3CO -> CH2CO -> CH2 -> CH. The rate-determining step is CH3CO dehydrogenation, with a reaction barrier of 0.52 eV. In addition, the formation and primary decomposition pathways of the critical intermediate acetone have also been investigated. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

引用

页码：330 / 339

页数：10

共 43 条

[1] Experimental and DFT studies of the conversion of ethanol and acetic acid on PtSn-based catalysts [J].

Alcala, R ;

Shabaker, JW ;

Huber, GW ;

Sanchez-Castillo, MA ;

Dumesic, JA .

JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (06) :2074-2085

[2] Hydrogen production via catalytic steam reforming of the aqueous fraction of bio-oil using nickel-based coprecipitated catalysts [J].

Bimbela, F. ;

Oliva, M. ;

Ruiz, J. ;

Garcia, L. ;

Arauzo, J. .

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 2013, 38 (34) :14476-14487

[3] Computational Investigation of Thermochemistry and Kinetics of Steam Methane Reforming on Ni(111) under Realistic Conditions [J].

Blaylock, D. Wayne ;

Ogura, Teppei ;

Green, William H. ;

Beran, Gregory J. O. .

JOURNAL OF PHYSICAL CHEMISTRY C, 2009, 113 (12) :4898-4908

[4] Review of fast pyrolysis of biomass and product upgrading [J].

Bridgwater, A. V. .

BIOMASS & BIOENERGY, 2012, 38 :68-94

[5] Understanding of ethanol decomposition on Rh(1 1 1) from density functional theory and kinetic Monte Carlo simulations [J].

Choi, YongMan ;

Liu, Ping .

CATALYSIS TODAY, 2011, 165 (01) :64-70

[6] Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Bronsted-Evans-Polanyi Relations [J].

Ferrin, P. ;

Simonetti, D. ;

Kandoi, S. ;

Kunkes, E. ;

Dumesic, J. A. ;

Norskov, J. K. ;

Mavrikakis, M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (16) :5809-5815

[7] The structure and reactivity of 2-butanol on Pd(111) [J].

Gao, Feng ;

Wang, Yilin ;

Burkholder, Luke ;

Hirschmugl, Carol ;

Saldin, Dilano K. ;

Poon, Hin Cheuk ;

Sholl, David ;

James, Joanna ;

Tysoe, Wilfred T. .

SURFACE SCIENCE, 2008, 602 (13) :2264-2270

[8] Catalytic steam reforming of bio-oils for the production of hydrogen: effects of catalyst composition [J].

Garcia, L ;

French, R ;

Czernik, S ;

Chornet, E .

APPLIED CATALYSIS A-GENERAL, 2000, 201 (02) :225-239

[9] Reaction kinetics measurements and analysis of reaction pathways for conversions of acetic acid, ethanol, and ethyl acetate over silica-supported Pt [J].

Gursahani, KI ;

Alcalá, R ;

Cortright, RD ;

Dumesic, JA .

APPLIED CATALYSIS A-GENERAL, 2001, 222 (1-2) :369-392

[10] A climbing image nudged elastic band method for finding saddle points and minimum energy paths [J].

Henkelman, G ;

Uberuaga, BP ;

Jónsson, H .

JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (22) :9901-9904

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