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DFT计算在铁基催化剂费托合成反应研究中的应用

何富贵 张曈 梁洁 李海鹏 何育荣 高新华 张建利 赵天生

何富贵, 张曈, 梁洁, 李海鹏, 何育荣, 高新华, 张建利, 赵天生. DFT计算在铁基催化剂费托合成反应研究中的应用[J]. 燃料化学学报(中英文), 2023, 51(11): 1540-1564. doi: 10.1016/S1872-5813(23)60366-4
引用本文: 何富贵, 张曈, 梁洁, 李海鹏, 何育荣, 高新华, 张建利, 赵天生. DFT计算在铁基催化剂费托合成反应研究中的应用[J]. 燃料化学学报(中英文), 2023, 51(11): 1540-1564. doi: 10.1016/S1872-5813(23)60366-4
HE Fu-gui, ZHANG Tong, LIANG Jie, LI Hai-peng, HE Yu-rong, GAO Xin-hua, ZHANG Jian-li, ZHAO Tian-sheng. Application of DFT calculation in the study of iron-based catalyst for Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology, 2023, 51(11): 1540-1564. doi: 10.1016/S1872-5813(23)60366-4
Citation: HE Fu-gui, ZHANG Tong, LIANG Jie, LI Hai-peng, HE Yu-rong, GAO Xin-hua, ZHANG Jian-li, ZHAO Tian-sheng. Application of DFT calculation in the study of iron-based catalyst for Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology, 2023, 51(11): 1540-1564. doi: 10.1016/S1872-5813(23)60366-4

DFT计算在铁基催化剂费托合成反应研究中的应用

doi: 10.1016/S1872-5813(23)60366-4
基金项目: 国家自然科学基金(22002008, 21965029),宁夏回族自治区重点研发计划(2022BEE03002, 2022BSB03056),宁夏自然科学基金(2022AAC03040),第四批宁夏青年科技人才托举工程(TJGC2019022)和中国科学院“西部之光”(XAB2019AW02)资助
详细信息
    通讯作者:

    E-mail: hyr@nxu.edu.cn

    gxh@nxu.edu.cn

  • 中图分类号: O643

Application of DFT calculation in the study of iron-based catalyst for Fischer-Tropsch synthesis

Funds: The project was supported by the National Natural Science Foundation of China (22002008, 21965029), Ningxia Key Research and Development Project (2022BEE03002, 2022BSB03056), the Natural Science Foundation of Ningxia (2022AAC03040), the Fourth Batch of Ningxia Youth Talents Supporting Program (TJGC2019022) and West Light Foundation of the Chinese Academy of Sciences (XAB2019AW02).
  • 摘要: 费托合成是煤炭间接液化的关键技术。铁基催化剂是常用的FTS催化剂。受反应过程中相变复杂性和原位表征困难的限制,密度泛函理论(DFT)成为研究铁基催化剂表面物种吸附和反应的必要手段。本工作以铁碳化合物的表面化学性质作为出发点,探讨了不同碳化铁物相的形成条件及表面物种吸附性能,简述了当前DFT计算研究涉及的FTS基元反应,总结了不同机制下链引发、链增长、链终止的机理研究。结合实验研究进展,总结了助剂的加入对铁基催化剂结构和性能的调控机理,结合一些前沿研究,对目前铁基催化剂存在的问题进行总结,对表面碳在催化反应中的作用和各物相催化作用差异等问题进行了展望。
  • FIG. 2758.  FIG. 2758.

    FIG. 2758.  FIG. 2758.

    图  1  氧化铁和碳化物组成的双官能活性位点上CO2加氢生成碳氢化合物的示意图[9]

    Figure  1  Scheme of CO2 hydrogenation to hydrocarbons at bifunctional active sites composed of iron oxide and carbide [9](with permission from ACS publications)

    图  2  理论计算、原位表征、催化实验在时间和空间尺度对比示意图

    Figure  2  Comparison of theoretical calculation, in-situ characterization and experimental at time and space scales

    图  3  金属铁和碳化铁的相互转化示意图

    Figure  3  Mutual transformation diagram of metallic iron and iron carbide

    图  4  (a) 链增长示意图,(b) ASF分布示意图[95,96]

    Figure  4  (a) Chain growth diagram, (b) ASF distribution diagram[95,96] (with permission from ACS publications)

    图  5  χ-Fe5C2表面CO活化机理示意图[100]

    Figure  5  Mechanism of CO activation on χ-Fe5C2 surface[100] (with permission from ACS publications)

    图  6  η-Fe2C(011)、(110)、(211)和(121)表面CO活化途径的能量[111]

    Figure  6  Energy diagram of CO activation pathway on η-Fe2C (011), (110), (211) and (121) surfaces Energy zero point is the total energy of free CO and H2 molecules Black line : mechanism I; red line : mechanism II, activate intermediates through *HCO; blue line : Mechanism II, activate intermediates through *COH[111] (with permission from ACS publications)

    图  7  (a) h-Fe7C3(211)表面4F2位点CO直接或H辅助解离途径CO活化机制的能量分布,(b) h-Fe7C3(1-11)表面CO直接或H辅助解离途径的构型和能量[107, 121]

    Figure  7  (a) The energy distribution of the CO activation mechanism over the 4F2 site via CO direct or H-assisted dissociation on the surface of h-Fe7C3(211). The configuration and energy of CO direct or H-assisted dissociation on (B) h-Fe7C3(111) surface[107, 121](purple : Fe atom ; gray : C atom; red : O atom ; yellow : H atom) (with permission from Molecular Catalysis and ACS publications)

    图  8  (a) 三种方式下甲烷化反应中所涉及的基本步骤的TS结构,(b) 三种情况下CH4形成的能量分布[125]

    Figure  8  (a) TS structure of the basic steps involved in the methanation reaction in three ways, Blue : iron atom; gray: C atom; green: C atom involved in the reaction; white: H atom; yellow: H atom involved in the reaction; (b) energy distribution of CH4 formation in three ways[125] (with permission from ACS publications)

    图  9  (a) χ-Fe5C2(510)表面CH + CO → CCH + O形成途径的能量和结构:碳化物机制(红色实线)和CO插入机制(蓝色虚线)(零点能量也包括在内,蓝色:铁原子;灰色:C原子;绿色:参与反应的C原子;白色:H原子;红色:O原子)(b) C1−C1偶联反应的有效势垒(Eeff, C−C)和反应势垒(Ea),以及对χ-Fe5C2(510)和χ-Fe5C2(100)表面的反应物能(Ei + Ej)[125]

    Figure  9  (a) The energy and structure of CH + CO → CCH + O formation pathway on χ-Fe5C2 (510) surface : carbide mechanism(red solid line) and CO insertion mechanism (blue dotted line). The zero energy is included (Blue: iron atom; gray: C atom; green: C atoms involved in the reaction; white: H atom; red: O atoms) (b) Effective barrier (Eeff, C−C) and the reaction barrier (Ea) for the C1−C1 coupling reaction, as well as the energies of reactant (Ei + Ej) for χ-Fe5C2(510) and χ-Fe5C2(100) surfaces[125] (with permission from ACS publications)

    图  10  pH2/pCO2条件下,各表面对Fe5C2颗粒的动力学贡献 (a) CH4组和 (b) C2 + [131]

    Figure  10  Kinetic contribution of each plane of Fe5C2 particles under = pH2/pCO2 conditions (a) CH4 and (b) C2 + pCO = 1.0 * 10−4 Pa and T = 550 K[131] (with permission from ACS publications)

    图  11  (a) CO和合成气预处理下Hägg碳化物的形貌(括号中给出的指标表示对应的米勒指数,指数的第二项提供了对应的表面a = Fe/C比,指数的第三项提供了每个暴露表面对总表面积的贡献);(b) 图(a)中构造的8个Wulff暴露表面对应碳化学势(μc)最稳定端的表面结构(图左括号中给出的指标表示每个表面的米勒指数,每个结构下的数字分别为对应表面a = Fe/C比,蓝球表示Fe原子,黑球表示C原子)[142]

    Figure  11  (a) Morphologies of Hägg carbide under CO and syngas pretreatments (indices given in parentheses indicates the corresponding Miller index. The second number is the corresponding surface Fe/C ratio. The third number is the contribution of each plane to the total surface area). (B) The most stable terminations of the structures from Wulff construction in Figure (a) at corresponding carbon chemical potential(mc) (indices on the left of the figure indicates the Miller index of each plane. The number under each structure is the corresponding surface Fe/C ratio, blueballs for Fe atoms and black balls for C atoms)[142] (with permission from ACS publications)

    图  12  催化剂活性与表面结合强度的关系[146]

    Figure  12  Relationship between catalyst activity and surface bonding strength[146] (with permission from ACS publications)

    图  13  (左)K在χ-Fe5C2(100)0.00上吸附后的电荷密度差图,显示以e/A3为单位的增加(橙色,红色)和减少(蓝色)区域;(a)中的采样平面穿过山谷并经过K,(b)中的采样平面穿过山谷并经过K;(右)预覆盖K的χ-Fe5C2(100)表面上O吸附电荷密度变化的(a)侧视图和(b)俯视图,红色(绿色)等值面表示增加(减少)0.015 e/A3;(c)χ-Fe5C2(100)上吸附K和吸附O相互作用时电荷密度变化的侧视图和(d)俯视图,红色(绿色)等值面表示增加(减少)0.005 e/A3,Fe和C原子分别为紫色和橙色,K和O的位置被标记[122]

    Figure  13  (left) The charge density difference of K adsorbed on χ-Fe5C2 (100)0.00 shown the increase (orange, red) or decrease (blue) regions in e/A3. The sampling plane in (a) crosses the valley and through K. The sampling plane in (b) crosses the valley and through K. (right) (a) side view and (b) top view of the change of O adsorption charge density on χ-Fe5C2(100) surface pre-covered with K. The red (green) isosurface indicates an increase (or decrease) of 0.015 e/A3. (c) The side view and (d) top view of the change of charge density in the interaction between adsorbed K and adsorbed O on χ-Fe5C2(100). The red (green) isosurface indicates an increase (decrease) of 0.005 e/A3. The Fe and C atoms are purple and orange, respectively. The positions of K and O are marked[122] (with permission from ACS publications)

    表  1  CO在ε-Fe2C、χ-Fe5C2θ-Fe3C、Fe3C7不同表面最稳定吸附位点吸附能、吸附位点键长、振动频率和不同暴露表面面积占总暴露表面面积比

    Table  1  Adsorption energy, bond length, vibration frequency and the ratio of different exposed surface area to the total exposed surface area of CO on the surfaces of ε-Fe2C, χ-Fe5C2, θ-Fe3C and Fe3C7

    SurfacesEads/eVSitesdC−OdFe−Cv(C−O)/cm−1ContributionsRef
    Fe(100)−1.071.321189[64]
    (110)−1.511.321172[65]
    (111)−1.171.201739[65]
    (210)−1.111.331115[65]
    (211)−1.061.281274[65]
    (310)0.911.331134[65]
    Fe2C(011)−2.0722F2.3091940[62]
    (110)−2.0741F-21.78118480.02[66]
    (211)−1.6232F-12.3291886[62]
    (121)−1.6654F2.001 2.090 2.184 2.24716000.39[66]
    (101)0.48[67]
    (001)−1.991F1.1401.760[68]
    Fe5C2(510)−2.053F11.2011.941 2.067 2.05217290.06[69]
    (100)−1.53T11.171.76419400.07[69]
    (010)−1.924F11.2121.911 2.018 2.272 2.41116590.07[69]
    (001)−1.863F11.2092.068 1.916 2.08316800.12[69]
    (110)−1.91T11.1691.78419430.13[69]
    (111)−1.51T11.1661.1719700.36[69]
    (11-1)−2.04T11.1761.76519030.10[70]
    (221)−2.005F21.2982.097 2.040 2.207 2.0391215[69]
    (411)−2.025F11.17918790.06[69]
    Fe3C(100)−1.773F1.2041.910 2.044 2.0180.03[70]
    (001)−1.794F1.2092.276 1.913 1.972 2.2970.07[71]
    (010)−2.032F1.1741.779 2.43319330.24[72]
    (111)0.44[73]
    Fe7C3(1-11)−3.03B51.3591.916 1.941 1.942 2.177[74]
    (001)−2.473F11.2021.997 1.984 1.989[74]
    (211)−2.37T6[75]
    (11-1)−2.274F31.221.949 1.957 2.269 2.344[75]
    (1-10)−2.162F21.1941.777 2.284[75]
    (101)−2.242F11.1961.857 1.949[75]
    Note: surface area contribution ratio was calculated at 550 K, 30 atm, ΔUc = −7.26 eV, H2/CO = 8
    下载: 导出CSV

    表  2  χ-Fe5C2不同表面O物种最稳定吸附构型吸附能、键长[84]

    Table  2  Adsorption energy and bond length of the most stable adsorption configuration of O species on different surfaces of χ-Fe5C2[84](with permission from ACS publications)

    SurfaceEads /eVdFe-OdC−O
    (510)−0.991.8701.8751.910
    (001)−0.761.8611.8931.936
    (010)−0.931.8611.8801.918
    (110)−0.351.7491.794
    (11-1)−0.981.8421.8891.977
    (-411)−1.111.8501.8871.919
    (111)−0.151.9881.267
    下载: 导出CSV

    表  3  χ-Fe5C2不同表面H和CHx物种吸附能[85]

    Table  3  Adsorption energies of H and CHx species on different surfaces of χ-Fe5C2[85](with permission from ACS publications)

    AdsorbateEads /eV
    (510)(021)(001)(100)
    H−0.69−0.62−0.61−0.72
    C−8.16−8.28−7.28−7.06
    CH−7.26−7.21−6.63−6.55
    CH2−4.48−4.48−4.22−4.36
    CH3−2.21−2.10−2.05−2.53
    下载: 导出CSV

    表  4  碳化物机理和CO插入机理对比[86]

    Table  4  Comparison of carbide mechanism and CO insertion mechanism[86](with permission from ACS publications)

    MechanismPresenterMechanism contentMerits and demeritsIntermediate
    Carbide mechanismFisher and TropschCO is first dissociated on the surface of the catalyst to form an active carbon species, which reacts with hydrogen to form methylene and then further polymerizes to form alkanes and olefinsIt can explain the formation of various hydrocarbons, but cannot explain the formation of oxygen-containing compounds and branched products.M-C



    CO insertion mechanism

    Pichler and Schulz
    After the formation of formyl group, CO and H2 are further hydrogenated to form bridged methylene species, which can be further hydrogenated to form carbonene and methyl, and CO is repeatedly inserted and hydrogenated in the intermediate to form various hydrocarbonsIn addition to explaining the formation process of linear hydrocarbons, it can also explain the formation process of oxygen-containing compounds, but it cannot explain the formation of branched products.
    下载: 导出CSV

    表  5  CO在四种铁碳化合物不同表面上的最稳定和最活跃位点上的解离、CO吸附位点、活化能(Ea)、反应能(ΔEr)、CO解离过渡态的键长(dC−O)汇总

    Table  5  CO dissociation, CO adsorption sites, activation energy (Ea), reaction energy (ΔEr), bond length of CO dissociation transition state (dC−O) at the most stable and active sites of CO on the surfaces of four iron-carbon compounds

    SurfaceMost stable configurationMost actived configuration
    sitesEa/eVΔEr/eVdC−OsitesEa/eVΔEr/eVdC−ORef
    Fe2C(011)2F2.49[104]
    (110)1F-23.47[101]
    (211)2F-12.69[101]
    (121)4F1.85[101]
    (001)1F−1.08[72]
    Fe5C2(510)3F12.571.061.795F10.87−0.911.72[69]
    (100)3F1.810.232F12.451.122.00[69]
    (010)4F11.54−0.092.005F11.49−0.142.00[69]
    (001)3F11.890.861.996F10.80−0.411.96[69]
    (110)3F1.890.991.832F31.491.022.09[69]
    (111)T12.950.951.944F12.000.311.94[69]
    (11-1)T12.810.712.026F10.830.141.86[69]
    (221)5F20.97−1.261.835F10.79−1.431.75[69]
    (-411)T12.900.731.884F11.37−0.282.04[69]
    Fe3C(100)3F1.68−0.53[102]
    (001)4F1.920.12[102]
    (010)2F1.200.28[102]
    (111)0.41−1.00[103]
    Fe7C3(1-11)B50.969−1.32[104]
    (001)3F11.480.144F20.91−1.10[105]
    (211)4F22.430.954F11.930.26[105]
    下载: 导出CSV

    表  6  η-Fe2C催化剂完美和缺陷表面CO活化的活化势垒(Ea)和所涉及表面铁原子的Bader电荷(qB)[113]

    Table  6  Activation barrier (Ea) of CO and the Bader charge (qB) of the involved surface Fe atoms on the perfect and defective surfaces of η-Fe2C catalyst[113](with permission from ACS publications)

    Perfect surfaceDefective surface
    011110211121011110211121
    Ea/eV2.443.152.611.650.871.001.030.88
    qB/e0.5350.5690.5130.5250.3470.4390.3920.379
    下载: 导出CSV

    表  7  χ-Fe5C2九个面CO解离IS(吸附CO和2H)的吸附能Eads和TSn对应的活化能Ea(n)[114]

    Table  7  Adsorption energy Eads and TSn corresponding activation energy Ea(n) of CO dissociation IS (adsorbed CO and 2H) over nine planes of χ-Fe5C2 [114](with permission from ACS publications)

    SurfaceSiteEads(IS)Ea(1)Ea(2)Ea(3)Ea(4)Ea(5)Ea(6)Ea(7)Ea(8)Ea(9)
    (001)ms−3.342.031.020.901.052.010.930.76
    ma−3.170.830.921.271.222.191.77
    (221)ms−3.771.131.190.480.641.871.09
    ma−3.730.991.240.330.881.56
    (510)ms−3.902.991.180.510.830.72
    ma−3.781.181.620.540.561.57
    (010)ms−3.631.890.960.560.641.830.650.07
    ma−3.391.530.720.560.641.830.650.071.86
    (110)ms−3.063.511.131.691.071.651.710.77
    ma−2.521.610.980.330.862.080.500.19
    (-411)ms−3.923.261.031.080.661.850.960.32
    ma−3.312.111.031.320.871.941.320.361.470.49
    (11-1)ms−3.483.641.010.990.191.521.120.23
    ma−2.560.960.510.810.641.600.462.190.91
    (111)ms−2.132.841.390.361.662.502.30
    ma−1.862.010.731.740.551.161.590.711.131.82
    (100)ms−2.393.001.111.150.161.101.390.83
    ma−1.182.860.281.130.501.331.220.51
    下载: 导出CSV

    表  8  θ-Fe3C九个表面H辅助机制活化能和反应能[120]

    Table  8  Activation and reaction energy of H-assisted mechanisms over nine planes of θ-Fe3C[120](with permission from ACS publications)

    SurfaceHCO-formationHCO-dissociationCOH-formationCOH-dissociation
    Ea/eVΔEa/eVEa/eVΔEa/eVEa/eVΔEa/eVEa/eVΔEa/eV
    (100)0.620.480.91−0.991.721.180.80−1.23
    (010)0.610.550.740.011.190.950.59−0.67
    (110)2.521.040.68−0.892.261.121.24−0.34
    (011)2.651.141.02−0.792.001.631.27−0.64
    (001)1.040.520.56−0.782.100.811.04−0.42
    (101)2.492.010.48−1.482.402.340.91−1.97
    (0-11)0.750.480.29−0.382.360.971.10−0.95
    (1-11)1.611.220.01−1.682.010.940.27−1.51
    (111)1.300.860.45−1.202.151.340.54−1.36
    下载: 导出CSV

    表  9  χ-Fe5C2表面CHx + CHy耦合的势垒和反应能[131]

    Table  9  Barrier and reaction energy of CHx + CHy coupling on χ-Fe5C2 planes[131](with permission from ACS publications)

    ReactionEa /eVΔEr /eV
    (510)(021)(001)(100)(510)(021)(001)(100)
    C + C1.591.911.181.451.231.210.390.71
    C + CH1.091.380.781.020.650.850.220.72
    C + CH21.091.310.891.090.150.620.410.78
    C + CH31.210.760.901.420.070.160.360.23
    CH + CH0.961.270.941.450.430.910.420.13
    CH + CH21.031.631.101.580.640.720.520.11
    CH + CH31.521.191.521.790.420.450.640.44
    CH2 + CH20.981.170.600.300.020.160.170.69
    CH2 + CH31.450.871.471.280.230.060.110.14
    下载: 导出CSV
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