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  • ISSN 1006-3080
  • CN 31-1691/TQ

CuFe (100)及(110)面上合成气制低碳醇碳链增长机理研究

王康明 张海涛 李涛

王康明, 张海涛, 李涛. CuFe (100)及(110)面上合成气制低碳醇碳链增长机理研究[J]. 华东理工大学学报(自然科学版), 2022, 48(2): 139-147. doi: 10.14135/j.cnki.1006-3080.20210127003
引用本文: 王康明, 张海涛, 李涛. CuFe (100)及(110)面上合成气制低碳醇碳链增长机理研究[J]. 华东理工大学学报(自然科学版), 2022, 48(2): 139-147. doi: 10.14135/j.cnki.1006-3080.20210127003
WANG Kangming, ZHANG Haitao, LI Tao. Carbon Chain Growth Mechanism of Higher Alcohols Formation from Syngas on CuFe (100) and (110)[J]. Journal of East China University of Science and Technology, 2022, 48(2): 139-147. doi: 10.14135/j.cnki.1006-3080.20210127003
Citation: WANG Kangming, ZHANG Haitao, LI Tao. Carbon Chain Growth Mechanism of Higher Alcohols Formation from Syngas on CuFe (100) and (110)[J]. Journal of East China University of Science and Technology, 2022, 48(2): 139-147. doi: 10.14135/j.cnki.1006-3080.20210127003

CuFe (100)及(110)面上合成气制低碳醇碳链增长机理研究

doi: 10.14135/j.cnki.1006-3080.20210127003
详细信息
    作者简介:

    王康明(1996—),男,安徽淮南人,硕士生,主要研究方向为催化反应工程。E-mail:1561409713@qq.com

    通讯作者:

    李 涛,E-mail:tli@ecust.edu.cn

  • 中图分类号: TQ032.4

Carbon Chain Growth Mechanism of Higher Alcohols Formation from Syngas on CuFe (100) and (110)

  • 摘要: CuFe混合催化剂是一种重要的合成气制低碳醇用催化剂。为深入了解合成气制低碳醇的反应机理,从量子尺度利用密度泛函理论(DFT)研究了CuFe混合催化剂两个主要表面(100)及(110)上的碳链增长机理。计算发现Cu在Fe (100)及Fe (110)面上倾向于单层聚集分布,CuFe (100)面上CO活化机理为H辅助CO生成CHO,随后逐步加氢生成CH2O和CH3O,CH3O更倾向于生成CH3OH,其碳链增长方式为CHO插入;CuFe (110)面上CO活化机理与(100)面上相同,H辅助CO加氢生成CHO,并不断加氢依次生成CH2O和CH3O,但CH3O更倾向于生成CH3,CH3进一步与CO耦合完成碳链的增长。

     

  • 图  1  (a) Fe (100)及(b) Fe (110)表面Cu原子排布

    Figure  1.  Distribution of Cu atom on (a) Fe (100) and (b) Fe (110) surfaces

    图  2  (a) CuFe (100)与(b) CuFe (110)表面模型及其吸附位

    Figure  2.  Surface models and adsorption sites of (a) CuFe (100) and (b) CuFe (110)

    图  3  (a)CuFe (100)及(b)CuFe (110)面上所有物种最稳定吸附构型

    Figure  3.  Most stable adsorption configuration of species on (a) CuFe (100) and (b) CuFe (110) surfaces

    图  4  (a) CuFe (100)与(b) CuFe (110)面上CO活化解离过程涉及的反应势能图与过渡态构型

    Figure  4.  Potential energy diagram and transition state configuration of the involved reaction in the CO dissociation process on (a) CuFe (100) and (b) CuFe (110) surfaces

    图  5  (a)CuFe (110)及(b)CuFe (110)面上CHx, CHxO, CHxOH物种形成过程涉及反应的势能图与过渡态构型

    Figure  5.  Potential energy diagram and transition state configuration of the involved reaction in CHx, CHxO, CHxOH species on (a) CuFe (100) and (b) CuFe (110) surfaces

    图  6  (a) CuFe (100)与(b) CuFe (110)面上碳链增长过程涉及反应的势能图与过渡态构型

    Figure  6.  Potential energy diagram and transition state configuration of the involved reaction in carbon chain growth process on (a) CuFe (100) and (b) CuFe (110) surfaces

    表  1  Cu原子排布方式不同时Fe (100)和Fe (110)表面的表面能

    Table  1.   Surface energy on Fe (100) and Fe (110) surfaces with different Cu atom distribution methods

    Fe (100)Esurf/(J·m−2Fe (110)Esurf/(J·m−2
    Cu06.32Cu07.60
    Cu45.91Cu37.14
    Cu4(2)5.98Cu3(2)7.39
    Cu85.61Cu66.76
    Cu8(2)5.66Cu6(2)6.95
    Cu125.18Cu96.36
    Cu12(2)5.32Cu9(2)6.41
    Cu164.98Cu125.94
    下载: 导出CSV

    表  2  CuFe (100)及CuFe (110)面上所有物种的最稳定吸附位及吸附能

    Table  2.   Most stable adsorption sites and adsorption energies of species on CuFe (100) and CuFe (110) surfaces

    SpeciesCuFe (100)CuFe (110)
    Adsorption siteEads/eVBonding atomAdsorption siteEads/eVBonding atom
    CHollow−7.50CLB−9.07C
    OHollow−6.10OLB−6.23O
    HHollow−2.88HTF−5.28H
    COHollow−1.61CTF−2.52C
    CHOBridge-Hollow-Bridge−2.28C,OTF-LB-TF−3.93C,O
    CH2OHollow−3.61C,OSB-TF-SB−4.67C,O
    CH3OHollow−2.37OLB−4.37O
    COHHollow−3.82CLB−5.09C
    CHOHBridge−3.10CLB-TF−4.06C
    CH2OHTop-Bridge-Top−2.41C,OT-SB-T−2.72C,O
    CH3OHTop-Hollow−1.24OT-TF−2.66C
    CHHollow−6.58CLB−6.78C
    CH2Hollow−4.50CLB−5.23C
    CH3Bridge−2.20CTF−3.72C
    CH4Top−0.38T
    C2H6Bridge-Top-Bridge−0.13TF-T-TF
    CH3COTop-Bridge-Top−3.85C,OT-SB−3.48C,O
    CH3CHOTop-Bridge−3.58OT-SB−4.16O
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-01-27
  • 网络出版日期:  2021-04-12
  • 刊出日期:  2022-04-22

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