A mechanistic study on the decomposition of a model bio-oil compound for hydrogen production over a stepped Ni surface: Formic acid

被引：14
作者：
Li, Xinbao [1 ]
Xuan, Kejie [1 ]
Zhu, Yingying [1 ]
Chen, Geng [1 ]
Yang, Guohua [1 ]
机构：
[1] Ningbo Univ, Fac Maritime & Transportat, Ningbo 315211, Zhejiang, Peoples R China
来源：
APPLIED SURFACE SCIENCE | 2018年 / 452卷
基金：
中国国家自然科学基金;
关键词：
DFT; Bio-oil; Catalytic reforming; Formic acid; Hydrogen production; Ni catalyst; DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; ELASTIC BAND METHOD; ACETIC-ACID; FAST PYROLYSIS; BIOMASS; DFT; CATALYSTS; METHANOL; OXIDATION;
D O I：
10.1016/j.apsusc.2018.05.049
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 obtain a clearer understanding of the catalytic bio-oil reforming mechanism, we performed density functional theory calculations on the decomposition of formic acid over a stepped Ni surface. Formic acid was selected as a model bio-oil compound. Fourteen elementary reactions were considered. All the zero-point-energy corrected activation energies and reaction energies were obtained. The kinetic parameters of the reaction rate constants and thermodynamic equilibrium constants in the temperature range of 300-1000 K were revealed. COOH formation and its subsequent dissociation are energetically easier than that of HCOO. When combined with kinetic modeling, the most preferable pathway for formic acid dissociation on the surface is HCOOH -> COOH -> CO. The rate-determining step is COOH dehydroxylation to CO, associating with an activation energy of 0.51 eV and a rate constant of 5.16 x 10(9) s(-1) at 773 K. In addition, HCOO will be slowly accumulated on the surface as the temperature rises. (C) 2018 Elsevier B.V. All rights reserved.
引用
收藏
页码：87 / 95
页数：9
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