Unraveling the role of Fe5C2 in CH4 formation during CO2 hydrogenation over hydrophobic iron catalysts

被引：20
作者：
Zhang, Zhenzhou [1 ]
Chen, Baojian [1 ]
Jia, Lingyu [1 ]
Liu, Wenqi [1 ]
Gao, Xinhua [2 ]
Gao, Jian [1 ]
Meng, Bo [1 ]
Tan, Yisheng [4 ]
He, Yurong [2 ,4 ]
Tu, Weifeng [1 ]
Han, Yi-Fan [1 ,3 ]
机构：
[1] Zhengzhou Univ, Engn Res Ctr Adv Funct Mat Mfg, Sch Chem Engn, Minist Educ, Zhengzhou 450001, Peoples R China
[2] Ningxia Univ, Sch Chem & Chem Engn, State Key Lab High Efficiency Utilizat Coal & Gree, Yinchuan 750021, Peoples R China
[3] East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China
[4] Chinese Acad Sci, Inst Coal Chem, State Key Lab Coal Convers, Taiyuan 030001, Peoples R China
来源：
APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2023年 / 327卷
基金：
中国国家自然科学基金;
关键词：
Hydrophobic iron catalyst; H2O partial pressure; Pathways of CH4 formation; Product distribution regulation; Reaction mechanisms; FISCHER-TROPSCH SYNTHESIS; TOTAL-ENERGY CALCULATIONS; CARBON-DIOXIDE; LOWER OLEFINS; MN PROMOTER; CHI-FE5C2; FE; ACTIVATION; DFT; METHANATION;
D O I：
10.1016/j.apcatb.2023.122449
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：
The production of value-added hydrocarbons by CO2 hydrogenation over iron (Fe) catalysts is an emerging platform reaction in CO2 utilization. However, CH4 forming in all hydrogenation reactions is undesirable. We focus on the role of Fe5C2 active species in CH4 formation during CO2 hydrogenation catalysis. Thus, Fe5C2 was manipulated by covering a hydrophobic shell to clarify the pathway of CH4 formation. By a combination of TPSR, in situ spectroscopies and DFT calculations, the variation in the mechanism of CH4 formation with the content of hydrophobic shell has been revealed. Meanwhile, the enhancement of H2O retention on the hydrophobic shell surface of Fe5C2 was found to inhibit the activation of CO2 by increasing energy barriers of C-C coupling re-actions. Deep insights into the tunable role of Fe5C2 in the formation of CH4 can help for the further design of high performance catalysts for this reaction.
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页数：12
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共 57 条
  • [1] PROJECTOR AUGMENTED-WAVE METHOD
    BLOCHL, PE
    [J]. PHYSICAL REVIEW B, 1994, 50 (24): : 17953 - 17979
  • [2] Charge-Tuned CO Activation over a χ-Fe5C2 Fischer-Tropsch Catalyst
    Chen, Bingxu
    Wang, Di
    Duan, Xuezhi
    Liu, Wei
    Li, Yefei
    Qian, Gang
    Yuan, Weikang
    Holmen, Anders
    Zhou, Xinggui
    Chen, De
    [J]. ACS CATALYSIS, 2018, 8 (04): : 2709 - 2714
  • [3] A DFT study of the chain growth probability in Fischer-Tropsch synthesis
    Cheng, Jun
    Hu, P.
    Ellis, Peter
    French, Sam
    Kelly, Gordon
    Lok, C. Martin
    [J]. JOURNAL OF CATALYSIS, 2008, 257 (01) : 221 - 228
  • [4] Chain growth mechanism in Fischer-Tropsch synthesis: A DFT study of C-C coupling over Ru, Fe, Rh, and Re surfaces
    Cheng, Jun
    Hu, P.
    Ellis, Peter
    French, Sam
    Kelly, Gordon
    Lok, C. Martin
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2008, 112 (15) : 6082 - 6086
  • [5] Selective Production of Aromatics Directly from Carbon Dioxide Hydrogenation
    Cui, Xu
    Gao, Peng
    Li, Shenggang
    Yang, Chengguang
    Liu, Ziyu
    Wang, Hui
    Zhong, Liangshu
    Sun, Yuhan
    [J]. ACS CATALYSIS, 2019, 9 (05) : 3866 - 3876
  • [6] Stability and Reactivity of ε-χ-θ Iron Carbide Catalyst Phases in Fischer-Tropsch Synthesis: Controlling μc
    de Smit, Emiel
    Cinquini, Fabrizio
    Beale, Andrew M.
    Safonova, Olga V.
    van Beek, Wouter
    Sautet, Philippe
    Weckhuysen, Bert M.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (42) : 14928 - 14941
  • [7] Deciphering Metal-Oxide and Metal-Metal Interplay via Surface Organometallic Chemistry: A Case Study with CO2 Hydrogenation to Methanol
    Docherty, Scott R.
    Coperet, Christophe
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (18) : 6767 - 6780
  • [8] Probing The Structure Evolution of Iron-Based Fischer-Tropsch to Produce Olefins by Operando Raman Spectroscopy
    Fu, Donglong
    Dai, Weiwei
    Xu, Xinchao
    Mao, Wei
    Su, Junjie
    Zhang, Zhengpai
    Shi, Bianfang
    Smith, Julian
    Li, Ping
    Xu, Jing
    Han, Yi-Fan
    [J]. CHEMCATCHEM, 2015, 7 (05) : 752 - 756
  • [9] Iron Particle Size Effects for Direct Production of Lower Olefins from Synthesis Gas
    Galvis, Hirsa M. Torres
    Bitter, Johannes H.
    Davidian, Thomas
    Ruitenbeek, Matthijs
    Dugulan, A. Iulian
    de Jong, Krijn P.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (39) : 16207 - 16215
  • [10] Hydrogenation of carbon dioxide over iron carbide prepared from alkali metal promoted iron oxalate
    Gnanamani, Muthu Kumaran
    Hamdeh, Hussein H.
    Shafer, Wilson D.
    Hopps, Shelley D.
    Davis, Burtron H.
    [J]. APPLIED CATALYSIS A-GENERAL, 2018, 564 : 243 - 249
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