From Understanding of Catalyst Functioning toward Controlling Selectivity in CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Catalysts

被引:0
|
作者
Yang, Qingxin
Kondratenko, Evgenii V.
机构
关键词
FISCHER-TROPSCH SYNTHESIS; FE5C2-ZNO CATALYSTS; IRON CATALYST; CONVERSION; PERFORMANCE; DEACTIVATION; INSIGHTS; PROPENE; OLEFINS; DESIGN;
D O I
10.1021/accountsmr.4c00160
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The conversion of carbon dioxide (CO2) with hydrogen (H-2), generated by renewable energy sources, into value-added products is a promising approach to meet future demands for sustainable development. In this context, the hydrogenation of CO2 (CO2-FTS) to higher hydrocarbons (C2+), lower olefins, and fuels should be mentioned in particular. These products are used in our daily lives but are currently produced by energy-intensive and CO2-emitting oil-based cracking processes. The environmental compatibility and abundance of iron (Fe) used in CO2-FTS catalysts are also relevant to sustainable development. The CO2-FTS reaction was inspired by the experience accumulated in long-term research on Fischer-Tropsch synthesis with CO (CO-FTS). A simple grafting of catalyst formulations and reaction mechanisms from CO-FTS to CO2-FTS has, however, been proven unsatisfactory, likely due to differences in surface adsorbates, chemical potentials of CO and CO2, and H2O partial pressure. These characteristics affect both the catalyst structure and the reaction pathways. Consequently, CO2-FTS provides higher CH4 selectivity but lower C2+-selectivity than does CO-FTS, which appeals to fundamental research to hinder CH4 formation. In this Account, our recent progress in identifying descriptors for purposeful catalyst design is highlighted. Different from the trial-and-error methods and chemist's intuition strategies commonly used for catalyst design, our initial efforts were devoted to a meta-analysis of literature data to identify catalyst property-performance relationships in CO2-FTS. The resulting hypotheses were experimentally validated and provided the basis for catalyst development. Our other distinguishing strategy is spatially resolved analyses of reaction-induced catalyst restructuring and reaction kinetics. As the catalyst composition changes downstream of the catalyst bed, it is critical to consider the respective profiles to establish proper correlations between the working catalyst phase and species and the kinetics of the formation of selective and unselective reaction products. The importance of in situ characterization studies for understanding reaction-induced catalyst restructuring is especially highlighted. We also demonstrate the power of transient kinetic methods, i.e., temporal analysis of products (TAP) and steady-state isotopic transient kinetic analysis (SSITKA), to identify the mechanism and microkinetics of the activation of CO2, CO, and H-2 that characterize the efficiency of iron carbides for CO2 hydrogenation. The SSITKA method is also instrumental in quantifying the abundance and lifetime of surface intermediates, leading to CO or CH4. The global network of product formation is further established by analyzing selectivity-conversion relationships to identify primary and secondary products. Our spatially and time-resolved analyses of catalyst composition and product formation rates can be useful for various heterogeneous reactions studied in plug flow reactors because the partial pressures of feed components and reaction products change along the catalyst bed. Such changes can result in spatial profiles of active phases/species. Combining catalyst structural features with kinetic/mechanistic information allowed us to elucidate the fundamentals of controlling catalyst activity and product selectivity and the mechanism of catalyst deactivation. We also present how the derived knowledge aids in the design of robust Fe-based catalysts, paving the way for the current studies one step closer to the implementation of more sustainable CO2 utilization.
引用
收藏
页数:15
相关论文
共 50 条
  • [1] Comparative Study on CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Bimetallic Catalysts
    Ratchprapa Satthawong
    Naoto Koizumi
    Chunshan Song
    Pattarapan Prasassarakich
    [J]. Topics in Catalysis, 2014, 57 : 588 - 594
  • [2] Comparative Study on CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Bimetallic Catalysts
    Satthawong, Ratchprapa
    Koizumi, Naoto
    Song, Chunshan
    Prasassarakich, Pattarapan
    [J]. TOPICS IN CATALYSIS, 2014, 57 (6-9) : 588 - 594
  • [3] Computational study of hydrocarbons synthesis from CO2 hydrogenation over Fe-based catalysts
    Nie, Xiaowa
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2019, 257
  • [4] CO2 Hydrogenation to Hydrocarbons over Fe-Based Catalysts: Status and Recent Developments
    Krausser, Laura
    Yang, Qingxin
    Kondratenko, Evgenii V.
    [J]. CHEMCATCHEM, 2024, 16 (13)
  • [5] CO2 hydrogenation to hydrocarbons over Co and Fe-based Fischer-Tropsch catalysts
    Visconti, Carlo Giorgio
    Martinelli, Michela
    Falbo, Leonardo
    Fratalocchi, Laura
    Lietti, Luca
    [J]. CATALYSIS TODAY, 2016, 277 : 161 - 170
  • [6] Development of Fe-based catalysts for CO2 hydrogenation to higher hydrocarbons for operating in slurry reactor
    Fedorov, Aleksandr
    Graefe, Philipp Andreas
    Perechodjuk, Anna
    Rauch, Reinhard
    Wohlrab, Sebastian
    Linke, David
    [J]. APPLIED CATALYSIS A-GENERAL, 2024, 680
  • [7] Hydrocarbons synthesis from CO2 hydrogenation over Fe-based catalysts: Reaction pathways and kinetics from DFT
    Nie, Xiaowa
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2018, 255
  • [8] Fe-based bimetallic catalysts supported on TiO2 for selective CO2 hydrogenation to higher hydrocarbons
    Boreriboon, Nuttakorn
    Wang, Wenjia
    Jiang, Xiao
    Song, Chunshan
    Prasassarakich, Pattarapan
    [J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2017, 254
  • [9] The role of Na for efficient CO2 hydrogenation to higher hydrocarbons over Fe-based catalysts under externally forced dynamic conditions
    Yang, Qingxin
    Lund, Henrik
    Bartling, Stephan
    Krumeich, Frank
    Skrypnik, Andrey S.
    Kondratenko, Evgenii, V
    [J]. JOURNAL OF CATALYSIS, 2023, 426 : 126 - 139
  • [10] Catalytic Hydrogenation of CO2 to Isoparaffins over Fe-Based Multifunctional Catalysts
    Wei, Jian
    Yao, Ruwei
    Ge, Qjngjie
    Wen, Zhiyong
    Ji, Xuewei
    Fang, Chuanyan
    Zhang, Jixin
    Xu, Hengyong
    Sun, Jian
    [J]. ACS CATALYSIS, 2018, 8 (11): : 9958 - 9967