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

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

何富贵^1,,
张曈^1,,
梁洁^1,,
李海鹏^1,,
何育荣^1, ,,
高新华^{1, 2, ,},
张建利^1,,
赵天生^1,

1.
宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏银川 750021
2.
国家能源集团宁夏煤业有限责任公司煤炭化学工业技术研究院, 宁夏银川 750411

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
计量
- 文章访问数: 2587
- HTML全文浏览量: 145
- PDF下载量: 135
- 被引次数: 0
出版历程
- 收稿日期: 2023-02-28
- 修回日期: 2023-04-01
- 录用日期: 2023-04-02
- 网络出版日期: 2023-05-06
- 刊出日期: 2023-11-13

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

HE Fu-gui^1
,,
ZHANG Tong^1
,,
LIANG Jie^1
,,
LI Hai-peng^1
,,
HE Yu-rong^{1
, ,},
GAO Xin-hua^{1, 2
, ,},
ZHANG Jian-li^1
,,
ZHAO Tian-sheng^1
,

1.
Ningxia University, School of Chemistry and Chemical Engineering, State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Yinchuan 750021, China
2.
Institute of Coal Chemical Industry Technology, National Energy Group Ningxia Coal Industry Co., Ltd., Yinchuan 750411, China

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

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。
- FTS反应 /
- 铁碳化物 /
- DFT计算 /
- 助剂
Abstract: Fischer-Tropsch synthesis (FTS) is the key technology of indirect coal liquefaction. Iron-based catalysts are commonly used. Due to the complexity of phase transition and the difficulty of in-situ characterization, density functional theory (DFT) has become a necessary means to study the adsorption and reaction of surface species on iron-based catalysts. In this review, the formation of different iron carbide phases and the adsorption properties of surface species were discussed based on the surface chemical properties of iron-carbon compounds. Then, the elementary reactions involved in the current DFT calculation research are briefly described. The research of chain initiation, chain growth, and chain termination under different mechanisms is summarized. Combined with the experimental research progress, the regulation mechanism of the promoters on the structure and performance of iron-based catalysts was reviewed. Finally, the existing problems of iron-based catalysts are summarized. The role of surface carbon in the reactions and the effects of various phases are prospected combined with recent results.
- FTS reaction /
- iron carbide /
- DFT calculation /
- promoters

HTML全文

FIG. 2758. FIG. 2758.

下载: 全尺寸图片幻灯片

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）

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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(E_{eff, C−C})和反应势垒(E_a)，以及对χ-Fe₅C₂(510)和χ-Fe₅C₂(100)表面的反应物能(E_i + E_j)^[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 (E_{eff, C−C}) and the reaction barrier (E_a) for the C₁−C₁ coupling reaction, as well as the energies of reactant (E_i + E_j) for χ-Fe₅C₂(510) and χ-Fe₅C₂(100) surfaces^[125] (with permission from ACS publications)

下载: 全尺寸图片幻灯片

图 10 在p_H₂/p_CO₂条件下，各表面对Fe₅C₂颗粒的动力学贡献 (a) CH₄组和 (b) C_{2 +}组^[131]

Figure 10 Kinetic contribution of each plane of Fe₅C₂ particles under = p_H₂/p_CO₂ conditions (a) CH₄ and (b) C_{2 +} p_CO = 1.0 * 10⁻⁴ Pa and T = 550 K^[131] (with permission from ACS publications)

下载: 全尺寸图片幻灯片

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(μ_c)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(m_c) (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)

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

表 1 CO在ε-Fe₂C、χ-Fe₅C₂、θ-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

	Surfaces	E_ads/eV	Sites	d_C−O/Å	d_Fe−C/Å	v_(C−O)/cm⁻¹	Contributions	Ref
Fe	(100)	−1.07	−	1.32	−	1189	−	[64]
	(110)	−1.51	−	1.32	−	1172	−	[65]
	(111)	−1.17	−	1.20	−	1739	−	[65]
	(210)	−1.11	−	1.33	−	1115	−	[65]
	(211)	−1.06	−	1.28	−	1274	−	[65]
	(310)	0.91	−	1.33	−	1134	−	[65]

Fe₂C	(011)	−2.072	2F	−	2.309	1940	−	[62]
	(110)	−2.074	1F-2	−	1.781	1848	0.02	[66]
	(211)	−1.623	2F-1	−	2.329	1886	−	[62]
	(121)	−1.665	4F	−	2.001 2.090 2.184 2.247	1600	0.39	[66]
	(101)	−	−	−	−	−	0.48	[67]
	(001)	−1.99	1F	1.140	1.760	−	−	[68]

Fe₅C₂	(510)	−2.05	3F1	1.201	1.941 2.067 2.052	1729	0.06	[69]
	(100)	−1.53	T1	1.17	1.764	1940	0.07	[69]
	(010)	−1.92	4F1	1.212	1.911 2.018 2.272 2.411	1659	0.07	[69]
	(001)	−1.86	3F1	1.209	2.068 1.916 2.083	1680	0.12	[69]
	(110)	−1.91	T1	1.169	1.784	1943	0.13	[69]
	(111)	−1.51	T1	1.166	1.17	1970	0.36	[69]
	(11-1)	−2.04	T1	1.176	1.765	1903	0.10	[70]
	(221)	−2.00	5F2	1.298	2.097 2.040 2.207 2.039	1215	−	[69]
	(411)	−2.02	5F1	1.179	−	1879	0.06	[69]

Fe₃C	(100)	−1.77	3F	1.204	1.910 2.044 2.018	−	0.03	[70]
	(001)	−1.79	4F	1.209	2.276 1.913 1.972 2.297	−	0.07	[71]
	(010)	−2.03	2F	1.174	1.779 2.433	1933	0.24	[72]
	(111)	−	−	−	−	−	0.44	[73]

Fe₇C₃	(1-11)	−3.03	B5	1.359	1.916 1.941 1.942 2.177	−	−	[74]
	(001)	−2.47	3F1	1.202	1.997 1.984 1.989	−	−	[74]
	(211)	−2.37	T6	−	−	−	−	[75]
	(11-1)	−2.27	4F3	1.22	1.949 1.957 2.269 2.344	−	−	[75]
	(1-10)	−2.16	2F2	1.194	1.777 2.284	−	−	[75]
	(101)	−2.24	2F1	1.196	1.857 1.949	−	−	[75]
Note: surface area contribution ratio was calculated at 550 K, 30 atm, ΔU_c = −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)

Surface	E_ads /eV	d_Fe-O /Å			d_C−O /Å
(510)	−0.99	1.870	1.875	1.910	−
(001)	−0.76	1.861	1.893	1.936	−
(010)	−0.93	1.861	1.880	1.918	−
(110)	−0.35	1.749	1.794	−	−
(11-1)	−0.98	1.842	1.889	1.977	−
(-411)	−1.11	1.850	1.887	1.919	−
(111)	−0.15	1.988	−	−	1.267

下载: 导出CSV

表 3 χ-Fe₅C₂不同表面H和CH_x物种吸附能^[85]

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

Adsorbate	E_ads /eV
Adsorbate	(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)

Mechanism	Presenter	Mechanism content	Merits and demerits	Intermediate
Carbide mechanism	Fisher and Tropsch	CO 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 olefins	It 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 hydrocarbons	In 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(E_a)、反应能(ΔE_r)、CO解离过渡态的键长(d_C−O)汇总

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

	Surface	Most stable configuration				Most actived configuration
	Surface	sites	E_a/eV	ΔE_r/eV	d_C−O/Å	sites	E_a/eV	ΔE_r/eV	d_C−O/Å	Ref
Fe₂C	(011)	2F	2.49	−	−	−	−	−	−	[104]
	(110)	1F-2	3.47	−	−	−	−	−	−	[101]
	(211)	2F-1	2.69	−	−	−	−	−	−	[101]
	(121)	4F	1.85	−	−	−	−	−	−	[101]
	(001)	1F	−1.08	−	−	−	−	−	−	[72]
Fe₅C₂	(510)	3F1	2.57	1.06	1.79	5F1	0.87	−0.91	1.72	[69]
	(100)	3F	1.81	0.23	−	2F1	2.45	1.12	2.00	[69]
	(010)	4F1	1.54	−0.09	2.00	5F1	1.49	−0.14	2.00	[69]
	(001)	3F1	1.89	0.86	1.99	6F1	0.80	−0.41	1.96	[69]
	(110)	3F	1.89	0.99	1.83	2F3	1.49	1.02	2.09	[69]
	(111)	T1	2.95	0.95	1.94	4F1	2.00	0.31	1.94	[69]
	(11-1)	T1	2.81	0.71	2.02	6F1	0.83	0.14	1.86	[69]
	(221)	5F2	0.97	−1.26	1.83	5F1	0.79	−1.43	1.75	[69]
	(-411)	T1	2.90	0.73	1.88	4F1	1.37	−0.28	2.04	[69]
Fe₃C	(100)	3F	1.68	−0.53	−	−	−	−	−	[102]
	(001)	4F	1.92	0.12	−	−	−	−	−	[102]
	(010)	2F	1.20	0.28	−	−	−	−	−	[102]
	(111)	−	0.41	−1.00	−	−	−	−	−	[103]
Fe₇C₃	(1-11)	B5	0.969	−1.32	−	−	−	−	−	[104]
	(001)	3F1	1.48	0.14	−	4F2	0.91	−1.10	−	[105]
	(211)	4F2	2.43	0.95	−	4F1	1.93	0.26	−	[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(E_a)和所涉及表面铁原子的Bader电荷(q_B)^[113]

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

Perfect surface					Defective surface
	011	110	211	121	011	110	211	121
E_a/eV	2.44	3.15	2.61	1.65	0.87	1.00	1.03	0.88
q_B/e	0.535	0.569	0.513	0.525	0.347	0.439	0.392	0.379

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E_ads和T_Sn对应的活化能E_a(n)^[114]

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

Surface	Site	E_ads(IS)	E_a(1)	E_a(2)	E_a(3)	E_a(4)	E_a(5)	E_a(6)	E_a(7)	E_a(8)	E_a(9)
(001)	ms	−3.34	2.03	1.02	0.90	1.05	2.01	0.93	0.76	−	−
(001)	ma	−3.17	0.83	0.92	1.27	1.22	2.19	−	−	1.77
(221)	ms	−3.77	1.13	1.19	0.48	0.64	−	−	−	1.87	1.09
(221)	ma	−3.73	0.99	1.24	0.33	0.88	−	−	−	1.56	−
(510)	ms	−3.90	2.99	1.18	0.51	0.83	−	0.72	−	−	−
(510)	ma	−3.78	1.18	1.62	0.54	0.56	1.57	−	−	−	−
(010)	ms	−3.63	1.89	0.96	0.56	0.64	1.83	0.65	0.07	−	−
(010)	ma	−3.39	1.53	0.72	0.56	0.64	1.83	0.65	0.07	1.86	−
(110)	ms	−3.06	3.51	1.13	1.69	1.07	1.65	1.71	0.77	−	−
(110)	ma	−2.52	1.61	0.98	0.33	0.86	2.08	0.50	0.19	−	−
(-411)	ms	−3.92	3.26	1.03	1.08	0.66	1.85	0.96	0.32	−	−
(-411)	ma	−3.31	2.11	1.03	1.32	0.87	1.94	1.32	0.36	1.47	0.49
(11-1)	ms	−3.48	3.64	1.01	0.99	0.19	1.52	1.12	0.23	−	−
(11-1)	ma	−2.56	0.96	0.51	0.81	0.64	1.60	−	0.46	2.19	0.91
(111)	ms	−2.13	2.84	−	1.39	0.36	1.66	2.50	2.30	−	−
(111)	ma	−1.86	2.01	0.73	1.74	0.55	1.16	1.59	0.71	1.13	1.82
(100)	ms	−2.39	3.00	1.11	1.15	0.16	1.10	1.39	0.83	−	−
(100)	ma	−1.18	2.86	0.28	1.13	0.50	1.33	1.22	0.51	−	−

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)

Surface	HCO-formation		HCO-dissociation		COH-formation		COH-dissociation
Surface	E_a/eV	ΔE_a/eV	E_a/eV	ΔE_a/eV	E_a/eV	ΔE_a/eV	E_a/eV	ΔE_a/eV
(100)	0.62	0.48	0.91	−0.99	1.72	1.18	0.80	−1.23
(010)	0.61	0.55	0.74	0.01	1.19	0.95	0.59	−0.67
(110)	2.52	1.04	0.68	−0.89	2.26	1.12	1.24	−0.34
(011)	2.65	1.14	1.02	−0.79	2.00	1.63	1.27	−0.64
(001)	1.04	0.52	0.56	−0.78	2.10	0.81	1.04	−0.42
(101)	2.49	2.01	0.48	−1.48	2.40	2.34	0.91	−1.97
(0-11)	0.75	0.48	0.29	−0.38	2.36	0.97	1.10	−0.95
(1-11)	1.61	1.22	0.01	−1.68	2.01	0.94	0.27	−1.51
(111)	1.30	0.86	0.45	−1.20	2.15	1.34	0.54	−1.36

下载: 导出CSV

表 9 χ-Fe₅C₂表面CH_x + CH_y耦合的势垒和反应能^[131]

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

Reaction	E_a /eV				ΔE_r /eV
Reaction	(510)	(021)	(001)	(100)	(510)	(021)	(001)	(100)
C + C	1.59	1.91	1.18	1.45	1.23	1.21	0.39	0.71
C + CH	1.09	1.38	0.78	1.02	0.65	0.85	0.22	0.72
C + CH₂	1.09	1.31	0.89	1.09	0.15	0.62	0.41	0.78
C + CH₃	1.21	0.76	0.90	1.42	0.07	0.16	0.36	0.23
CH + CH	0.96	1.27	0.94	1.45	0.43	0.91	0.42	0.13
CH + CH₂	1.03	1.63	1.10	1.58	0.64	0.72	0.52	0.11
CH + CH₃	1.52	1.19	1.52	1.79	0.42	0.45	0.64	0.44
CH₂ + CH₂	0.98	1.17	0.60	0.30	0.02	0.16	0.17	0.69
CH₂ + CH₃	1.45	0.87	1.47	1.28	0.23	0.06	0.11	0.14

下载: 导出CSV

参考文献(172)

[1]	POROSOFF M D, YAN B, CHEN J G. Catalytic reduction of CO₂ by H₂ for synthesis of CO, methanol and hydrocarbons: Challenges and opportunities[J]. Energy Environ,2016,9(1):62−73. doi: 10.1039/C5EE02657A
[2]	YE R P, DING J, GONG W, ARGYLE M D, ZHONG Q, WANG Y, YAO Y G. CO₂ hydrogenation to high-value products via heterogeneous catalysis[J]. Nat Commun,2019,10(1):1−15. doi: 10.1038/s41467-018-07882-8
[3]	PRINZ R, SPINELLI R, MAGAGNOTTI N, ROUTA J, ASIKAINEN A. Modifying the settings of CTL timber harvesting machines to reduce fuel consumption and CO₂ emissions[J]. J Clean Prod,2018,197:208−217. doi: 10.1016/j.jclepro.2018.06.210
[4]	FISCHER F, TROPSCH H. The preparation of synthetic oil mixtures (synthyol) from carbon monoxide and hydrogen[J]. Brennstoff-Chemie,1923,4:276−285.
[5]	DE BEER M, KUNENE A, NABAHO D, CLAEYS M, VAN STEEN E. Technical and economic aspects of promotion of cobalt-based Fischer-Tropsch catalysts by noble metals-a review[J]. J S Afr I Min Metell,2014,114(2):157−165.
[6]	SUO Y, YAO Y, ZHANG Y, XING S, YUAN Z Y. Recent advances in cobalt-based Fischer-Tropsch synthesis catalysts[J]. J Ind Eng Chem , 2022.
[7]	GLASSER D, HILDEBRANDT D, LIU X, LU X, MASUKU C M. Recent advances in understanding the Fischer-Tropsch synthesis (FTS) reaction[J]. Curr Opin Chem Eng,2012,1(3):296−302. doi: 10.1016/j.coche.2012.02.001
[8]	ANANTHARAJ S, KUNDU S, NODA S. “The Fe Effect”: A review unveiling the critical roles of Fe in enhancing OER activity of Ni and Co based catalysts[J]. Nano Energy,2021,80:105514. doi: 10.1016/j.nanoen.2020.105514
[9]	NIE X, MENG L, WANG H, CHEN Y, GUO X, SONG C. DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO₂ over Fe-based catalysts[J]. Phys Chem Chem Phys,2018,20(21):14694−14707. doi: 10.1039/C8CP02218F
[10]	VAN DYK J C, KEYSER M J, COERTZEN M. Syngas production from South African coal sources using Sasol-Lurgi gasifiers[J]. Int J Coal Geol, 2006, 65(3/4): 243–253.
[11]	KIM K Y, LEE H, NOH, W Y, SHIN J, HAN S J, KIM S K, LEE J S. Cobalt ferrite nanoparticles to form a catalytic Co-Fe alloy carbide phase for selective CO₂ hydrogenation to light olefins[J]. ACS Catal,2020,10(15):8660−8671. doi: 10.1021/acscatal.0c01417
[12]	VAN STEEN E, CLAEYS M. Fischer-Tropsch catalysts for the biomass-to-liquid (BTL)-process[J]. Chem Eng Technol,2008,31(5):655−666. doi: 10.1002/ceat.200800067
[13]	XIE J, YANG J, DUGULAN A I, HOLMEN A, CHEN D, DE JONG K P, LOUWERSE M J. Size and promoter effects in supported iron Fischer-Tropsch catalysts: Insights from experiment and theory[J]. ACS Catal,2016,6(5):3147−3157. doi: 10.1021/acscatal.6b00131
[14]	JÄGER C, MUTSCHKE H, HUISKEN F, ALEXANDRESCU R, MORJAN I, DUMITRACHE F, SCHNEEWEISS O. Iron-carbon nanoparticles prepared by CO₂ laser pyrolysis of toluene and iron pentacarbonyl[J]. Appl Phys A,2006,85:53−62. doi: 10.1007/s00339-006-3665-2
[15]	KHOURY G A, SULLIVAN P J E. Research at imperial college on the effect of elevated temperatures on concrete[J]. Fire Saf J,1988,13(1):69−72. doi: 10.1016/0379-7112(88)90034-3
[16]	WANG Y, LIU S, HUANG P, XIE H, QIAO X. Structural and magnetic properties of mono-dispersed iron carbide (Fe_xC_y) nanoparticles synthesized by facile gas phase reaction[J]. Ceram Int,2019,45(8):11119−11124. doi: 10.1016/j.ceramint.2019.02.116
[17]	WANG D, XIE Z, POROSOFF M D, CHEN J G. Recent advances in carbon dioxide hydrogenation to produce olefins and aromatics[J]. Chem,2021,7(9):2277−2311. doi: 10.1016/j.chempr.2021.02.024
[18]	SUN J, CHEN Y, CHEN J. Towards stable Fe-based catalysts with suitable active phase for Fischer-Tropsch synthesis to lower olefins[J]. Catal Commun,2017,91:34−37. doi: 10.1016/j.catcom.2016.12.008
[19]	SHROFF M D, KALAKKAD D S, COULTER K E, KOHLER S D, HARRINGTON M S, JACKSON N B, DATYE A K. Activation of precipitated iron Fischer-Tropsch synthesis catalysts[J]. J Catal,1995,156(2):185−207. doi: 10.1006/jcat.1995.1247
[20]	梁洁, 王欣宇, 高新华, 田菊梅, 段斌, 张伟, 江永军, Prasert Reubroycharoen, 张建利, 赵天生. Fe基催化剂物相演变及CO₂加氢反应性能影响[J]. 燃料化学学报, 2022, 50(12): 1573–1580. LIANG Jie, WANG Xin-yu, GAO Xin-hua, TIAN Ju-mei, DUAN Bin, ZHANG Wei, JIANG Yong-jun, REUBROYCHAROEN Prasert, ZHANG Jian-li, ZHAO Tian-sheng. Effect of Na promoter and reducing atmosphere on phase evolution of Fe-based catalyst and its CO₂ hydrogenation performance[J] J Fuel Chem Technol, 2022, 50(12): 1573–1580.
[21]	ALAYAT A, MCLLROY D N, MCDONALD A G. Effect of synthesis and activation methods on the catalytic properties of silica nanospring (NS)-supported iron catalyst for Fischer-Tropsch synthesis[J]. Fuel Process Technol,2018,169:132−141. doi: 10.1016/j.fuproc.2017.09.011
[22]	TAHARI M N A, SALLEH F, SAHARUDDIN T S T, SAMSURI A, SAMIDIN S, YARMO M A. Influence of hydrogen and carbon monoxide on reduction behavior of iron oxide at high temperature: Effect on reduction gas concentrations[J]. Int J Hydrogen Energy,2021,46(48):24791−24805. doi: 10.1016/j.ijhydene.2020.06.250
[23]	MA Z, ZHOU C, WANG D, WANG Y, HE W, TAN Y, LIU Q. Co-precipitated Fe-Zr catalysts for the Fischer-Tropsch synthesis of lower olefins (C₂⁼−C₄⁼): Synergistic effects of Fe and Zr[J]. J Catal,2019,378:209−219. doi: 10.1016/j.jcat.2019.08.037
[24]	GAO R, LIU X, CAO Z, LIU X W, LU K, MA D, WEN X D. Carbon permeation: the prerequisite elementary step in iron-catalyzed Fischer-Tropsch synthesis[J]. J Catal,2019,149:645−664.
[25]	RUNXIA H. E, JIANG H, FANG W U, KEDUAN Z H I, NA W A N G, CHENLIANG Z H O U, QUANSHENG L I U. Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction[J]. J Rare Earth,2014,32(4):298−305. doi: 10.1016/S1002-0721(14)60071-5
[26]	TANG L, HE L, WANG, Y, CHEN B, XU W, DUAN, X, LU A H. Selective fabrication of χ-Fe₅C₂ by interfering surface reactions as a highly efficient and stable Fischer-Tropsch synthesis catalyst[J]. Appl Catal B: Environ,2021,284:119753. doi: 10.1016/j.apcatb.2020.119753
[27]	LIGER E, CHARLET L, VAN CAPPELLEN P. Surface catalysis of uranium (VI) reduction by iron (II)[J]. Geochim Cosmochim Acta, 1999, 63(19/20): 2939–2955.
[28]	KIM D H, HAN S W, YOON H S, KIM Y D. Reverse water gas shift reaction catalyzed by Fe nanoparticles with high catalytic activity and stability[J]. J Ind Eng Chem,2015,23:67−71. doi: 10.1016/j.jiec.2014.07.043
[29]	TRAN F, BLAHA P, SCHWARZ K, NOVÁK P. Hybrid exchange-correlation energy functionals for strongly correlated electrons: Applications to transition-metal monoxides[J]. Phys Rev B,2006,74(15):155108. doi: 10.1103/PhysRevB.74.155108
[30]	MENG Y, LIU X W, HUO C F, GUO W P, CAO D B, PENG Q, WEN X D. When density functional approximations meet iron oxides[J]. J Chem Theory Comput,2016,12(10):5132−5144. doi: 10.1021/acs.jctc.6b00640
[31]	WEZENDONK T A, SUN X, DUGULAN A I, VAN HOOF A J, HENSEN E J, KAPTEIJN F, GASCON J. Controlled formation of iron carbides and their performance in Fischer-Tropsch synthesis[J]. J Catal,2018,362:106−117. doi: 10.1016/j.jcat.2018.03.034
[32]	AMAYA-RONCANCIO S, LINARES D H, DUARTE H A, SAPAG K. DFT study of hydrogen-assisted dissociation of CO by HCO, COH, and HCOH formation on Fe(100)[J]. J Phys Chem C,2016,120(20):10830−10837. doi: 10.1021/acs.jpcc.5b12014
[33]	LIU J, ZHANG G, JIANG X, WANG J, SONG C, GUO X. Insight into the role of Fe₅C₂ in CO₂ catalytic hydrogenation to hydrocarbons[J]. Catal Today,2021,371:162−170. doi: 10.1016/j.cattod.2020.07.032
[34]	QIN S, ZHANG C, XU J, YANG Y, XIANG H, LI Y. Fe-Mo interactions and their influence on Fischer-Tropsch synthesis performance[J]. Appl Catal A: Gen,2011,392(1/2):118−126. doi: 10.1016/j.apcata.2010.10.032
[35]	DLAMINI H, MOTJOPE T, JOORST G, TER STEGE G, MDLELENI M. Changes in physico-chemical properties of iron-based Fischer–Tropsch catalyst induced by SiO₂ addition[J]. Catal Lett,2002,78:201−207. doi: 10.1023/A:1014953201451
[36]	LU K, HUO C F, GUO W P, LIU X W, ZHOU Y, PENG Q, WEN X D. Development of a reactive force field for the Fe-C interaction to investigate the carburization of iron[J]. Phys Chem Chem Phys,2018,20(2):775−783. doi: 10.1039/C7CP05958B
[37]	LIU Q Y, SHANG C, LIU Z P. In situ active site for CO activation in Fe-catalyzed Fischer-Tropsch synthesis from machine learning[J]. J Am Chem Soc,2021,143(29):11109−11120. doi: 10.1021/jacs.1c04624
[38]	王健. 费托合成催化剂活性相调控及其反应性能研究[D]. 天津: 天津大学, 2019. WANG Jian. Modulation of active phase and influences on catalytic performance for Fischer-Tropsch synthesis[D]. Tianjin: Tianjin University, 2019.
[39]	CHANG Q, ZHANG C, LIU C, WEI Y, CHERUVATHUR A V, DUGULAN A I, LI Y. Relationship between iron carbide phases (ε-Fe₂C, Fe₇C₃, and χ-Fe₅C₂) and catalytic performances of Fe/SiO₂ Fischer-Tropsch catalysts[J]. ACS Catal,2018,8(4):3304−3316. doi: 10.1021/acscatal.7b04085
[40]	TAN P. Active phase, catalytic activity, and induction period of Fe/zeolite material in nonoxidative aromatization of methane[J]. J Catal,2016,338:21−29. doi: 10.1016/j.jcat.2016.01.027
[41]	FANG C M, VAN HUIS M A, ZANDBERGEN H W. Structure and stability of Fe₂C phases from density-functional theory calculations[J]. Scr Mater,2010,63(4):418−421. doi: 10.1016/j.scriptamat.2010.04.042
[42]	宋楠. 低温费-托合成Fe₂C催化剂上合成气转化反应机理研究[D]. 上海: 华东理工大学, 2020. SONG Nan, A Theoretical study of the syngas conversion mechanism on Fe₂C catalysts for low-temperature Fischer-Tropsch synthesis[D]. Shanghai: East China University of Science and Technology, 2020.
[43]	LAI J, HUANG B, TANG Y, LIN F, ZHOU P, CHEN X, GUO S. Barrier-free interface electron transfer on PtFe-Fe₂C janus-like nanoparticles boosts oxygen catalysis[J]. Chem,2018,4(5):1153−1166. doi: 10.1016/j.chempr.2018.02.010
[44]	ZUO L, ZHANG Y D, HU Z C, FARAOUN H I, ZHAO X, ESLING C. Microstructural modification of metallic materials by electromagnetic processing and the theoretical interpretation[C]. Adv Mat Res. Trans Tech Publications Ltd, 2007, 29: 123–126.
[45]	SCHNEIDER A, INDEN G, GRABKE H J, WEI Q, PIPPEL E, WOLTERSDORF J. Effect of H₂S on formation and decomposition of Fe₃C and Fe₅C₂ under metal dusting conditions[J]. Steel Res Int,2000,71(5):179−184. doi: 10.1002/srin.200005710
[46]	YANG C, ZHAO H, HOU Y, MA D. Fe₅C₂ nanoparticles: A facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis[J]. J Am Chem Soc,2012,134(38):15814−15821. doi: 10.1021/ja305048p
[47]	CHA S, KIM H, CHOI H, KIM C S, HA K S. Effects of silica shell encapsulated nanocrystals on active χ-Fe₅C₂ phase and Fischer-Tropsch synthesis[J]. J Nanomater,2022,12(20):3704. doi: 10.3390/nano12203704
[48]	GAO Y, LIU S, ZHAO Z, TAO H, SUN Z. Heterogeneous catalysis of CO₂ hydrogenation to C₂⁺ products[J]. Acta Phys -Chim Sin,2018,34(8):858−872. doi: 10.3866/PKU.WHXB201802061
[49]	CAO D B, ZHANG F Q, LI Y W, WANG J, JIAO H. Structures and energies of coadsorbed CO and H₂ on Fe₅C₂(001), Fe₅C₂(110), and Fe₅C₂(100)[J]. J Phys Chem B,2005,109(21):10922−10935. doi: 10.1021/jp050940b
[50]	VENEGAS R, ZÚÑIGA C, ZAGAL J H, TORO-LABBÉ A, MARCO J F, MENÉNDEZ N, RECIO F J. Fe₃O₄ templated pyrolyzed Fe-N-C catalysts. Understanding the role of N-functions and Fe₃C on the ORR activity and mechanism[J]. ChemElectroChem,2022,9(11):e202200115.
[51]	HU Y, JENSEN J O, ZHANG W, HUANG Y, CLEEMANN L N, XING W, LI Q. Direct synthesis of Fe₃C-functionalized graphene by high temperature autoclave pyrolysis for oxygen reduction[J]. ChemSusChem,2014,7(8):2099−2103. doi: 10.1002/cssc.201402183
[52]	LIU Y, CHEN J F, BAO J, ZHANG Y. Manganese-modified Fe₃O₄ microsphere catalyst with effective active phase of forming light olefins from syngas[J]. ACS catal,2015,5(6):3905−3909. doi: 10.1021/acscatal.5b00492
[53]	TSUZUKI A, SAGO S, HIRANO S I, NAKA S. High temperature and pressure preparation and properties of iron carbides Fe₇C₃ and Fe₃C[J]. J Mater Sci,1984,19(8):2513−2518. doi: 10.1007/BF00550805
[54]	ZHANG J, ABBAS M, ZHAO, W, CHEN J. Enhanced stability of a fused iron catalyst under realistic Fischer-Tropsch synthesis conditions: insights into the role of iron phases (χ-Fe₅C₂, θ-Fe₃C and α-Fe)[J]. Catal Sci Technol,2022,12(13):4217−4227.
[55]	ZHANG M, GUAN X, YU Y. Theoretical insights into the removal pathways of adsorbed oxygen on the surface of χ-Fe₅C₂ (510)[J]. Chem Eng Sci,2023,271:118576.
[56]	LI W Q, ARCE-RAMOS J M, SULLIVAN M B, POH, C K, CHEN L, BORGNA A, ZHANG J. Mechanistic insights into selective ethylene formation on the χ-Fe₅C₂ (510) surface[J]. J Catal,2023,421:185−193.
[57]	DAVIS B H, XU L, BAO S. Role of CO₂ oxygenates and alkenes in the initiation of chain growth during the Fischer-Tropsch synthesis[J]. Stud Surf Sci Catal, 1997, 107: 175−180.
[58]	DE SMIT E, CINQUINI F, BEALE A M, SAFONOVA O V, VAN BEEK W, SAUTET P, WECKHUYSEN B M. Stability and reactivity of ϵ-χ-θ iron carbide catalyst phases in Fischer-Tropsch synthesis: Controlling μ_C[J]. J Am Chem Soc,2010,132(42):14928−14941. doi: 10.1021/ja105853q
[59]	LIU X, LIU J, YANG Y, LI Y W, WEN X. Theoretical perspectives on the modulation of carbon on transition-metal catalysts for conversion of carbon-containing resources[J]. ACS Catal,2021,11(4):2156−2181. doi: 10.1021/acscatal.0c04739
[60]	NØRSKOV J K, STUDT F, ABILD-PEDERSEN F, BLIGAARD T. Fundamental Concepts in Heterogeneous Catalysis[M]. Hoboken: John Wiley and Sons, 2014.
[61]	YU X, ZHANG X, WANG H, FENG G. High coverage water adsorption on the CuO(111) surface[J]. Appl Surf Sci,2017,425:803−810. doi: 10.1016/j.apsusc.2017.07.086
[62]	HAMMER B, NøRSKOV J K. Electronic factors determining the reactivity of metal surfaces[J]. Surf Sci,1995,343(3):211−220. doi: 10.1016/0039-6028(96)80007-0
[63]	WANG T, TIAN X, LI Y W, WANG J, BELLER M, JIAO H. High coverage CO activation mechanisms on Fe(100) from computations[J]. J Phys Chem C,2014,118(2):1095−1101.
[64]	LI T, WEN X, LI Y W, JIAO H. Mechanistic insight into CO activation, methanation and CC bond formation from coverage dependent CO hydrogenation on Fe(110)[J]. Surf Sci,2019,689:121456. doi: 10.1016/j.susc.2019.121456
[65]	WANG T, TIAN X X, LI Y W, WANG J, BELLER M, JIAO H. Coverage-dependent CO adsorption and dissociation mechanisms on iron surfaces from DFT computations[J]. ACS Catal,2014,4(6):1991−2005.
[66]	HE S, WANG W, SHEN Z, LI G, KANG J, LIU Z, WANG Y. Carbon nanotube-supported bimetallic Cu-Fe catalysts for syngas conversion to higher alcohols[J]. Mol Catal,2019,479:110610. doi: 10.1016/j.mcat.2019.110610
[67]	LYU S, WANG L, LI Z, YIN S, CHEN J, ZHANG Y, WANG Y. Stabilization of ε-iron carbide as high-temperature catalyst under realistic Fischer–Tropsch synthesis conditions[J]. Nat Commun,2020,11(1):6219. doi: 10.1038/s41467-020-20068-5
[68]	REDA M, HANSEN H A, VEGGE T. DFT study of the oxygen reduction reaction on carbon-coated iron and iron carbide[J]. ACS Catal,2018,8(11):10521−10529. doi: 10.1021/acscatal.8b02167
[69]	HE Y, ZHAO P, MENG Y, GUO W, YANG Y, LI Y W, WEN X D. Hunting the correlation between Fe₅C₂ surfaces and their activities on CO: The descriptor of bond valence[J]. J Phys Chem C,2018,122(5):2806−2814. doi: 10.1021/acs.jpcc.7b11430
[70]	BROOS R J, ZIJLSTRA B, FILOT I A, HENSEN E J. Quantum-chemical DFT study of direct and H-and C-assisted CO dissociation on the χ-Fe₅C₂ Hägg carbide[J]. J Phys Chem C,2018,122(18):9929−9938. doi: 10.1021/acs.jpcc.8b01064
[71]	CANO L A, BLANCO A G, LENER G, MARCHETTI S G, SAPAG K. Effect of the support and promoters in Fischer-Tropsch synthesis using supported Fe catalysts[J]. Catal Today,2017,282:204−213. doi: 10.1016/j.cattod.2016.06.054
[72]	YU X, ZHANG X, MENG Y, ZHAO Y, LI Y, XU W, LIU Z. CO adsorption, dissociation and coupling formation mechanisms on Fe₂C(001) surface[J]. Appl Surf Sci,2018,434:464−472. doi: 10.1016/j.apsusc.2017.10.225
[73]	韩光秀. χ-Fe₅C₂晶面对CO₂吸附活化及加氢转化影响的密度泛函理论研究[D]. 大连: 大连理工大学, 2022. HAN Guang-xiu. DFT study of the effect of crystal plane on CO₂ adsorption, activation, and hydrogenation over χ-Fe₅C₂ catalyst[D]. Dalian: Dalian University of Technology, 2022.
[74]	YONG Z, ZHU Z, WANG Z, HU J, PAN Q. One-dimensional carbon nanotube-Fe_xC_y nanocrystal composite[J]. Nanotechnology,2007,18(10):105602. doi: 10.1088/0957-4484/18/10/105602
[75]	LIU X W, HUO C F, LI Y W, WANG J, JIAO H. Energetics of carbon deposition on Fe(100) and Fe(110) surfaces and subsurfaces[J]. Surf Sci, 2012, 606(7/8): 733–739.
[76]	SALEH A A, CASILLAS G, PERELOMA E V, CARPENTER K R, KILLMORE C R, GAZDER A A. A transmission Kikuchi diffraction study of cementite in a quenched and tempered steel[J]. Mater Charact,2016,114:146−150. doi: 10.1016/j.matchar.2016.02.016
[77]	LIAO X Y, WANG S G, MA Z Y, WANG J, LI Y W, JIAO H. Density functional theory study of CO adsorption on the (100), (001) and (010) surfaces of Fe₃C[J]. J Mol Catal A: Chem, 2007, 269(1/2): 169–178.
[78]	FU J, SUN D, CHEN Z, ZHANG J, DU H. First-Principles Investigation of CO Adsorption on h-Fe₇C₃ Catalyst[J]. Crystals,2020,10(8):635. doi: 10.3390/cryst10080635
[79]	ZHANG M, REN J, YU Y. Investigating the CO activation mechanism on hcp-Fe₇C₃(211) via density functional theory[J]. Mol Catal,2021,505:111506. doi: 10.1016/j.mcat.2021.111506
[80]	PETERSEN M A, VAN DEN BERG J A, VAN RENSBURG W J. Role of step sites and surface vacancies in the adsorption and activation of CO on χ-Fe₅C₂ surfaces[J]. J Phys Chem C,2010,114(17):7863−7879. doi: 10.1021/jp911725u
[81]	BAI Y, LIU J, WANG T, SONG Y F, YANG Y, LI Y W, WEN X. Theoretical study about adsorbed oxygen reduction over χ-Fe₅C₂: Formation of H₂O and CO₂[J]. Mol Catal,2022,524:112236. doi: 10.1016/j.mcat.2022.112236
[82]	BENZIGER J, MADIX R J. The effects of carbon, oxygen, sulfur and potassium adlayers on CO and H₂ adsorption on Fe(100)[J]. Surf Sci,1980,94(1):119−153. doi: 10.1016/0039-6028(80)90160-0
[83]	SEIP U, BASSIGNANA I C, KÜPPERS J, ERTL G. A TDS and HREELS study of CO adsorbed on a potassium promoted Fe(111) surface[J]. Surf Sci,1985,160(2):400−418. doi: 10.1016/0039-6028(85)90783-6
[84]	BłOŃSKI P, KIEJNA A, HAFNER J. Theoretical study of oxygen adsorption at the Fe(110) and(100) surfaces[J]. Surf Sci,2005,590(1):88−100. doi: 10.1016/j.susc.2005.06.011
[85]	NIE X, WANG H, JANIK M J, CHEN Y, GUO X, SONG C. Mechanistic insight into C–C coupling over Fe-Cu bimetallic catalysts in CO₂ hydrogenation[J]. J Phys Chem C,2017,121(24):13164−13174. doi: 10.1021/acs.jpcc.7b02228
[86]	CHENG J, HU P, ELLIS P, FRENCH S, KELLY G, LOK C M. Some understanding of Fischer-Tropsch synthesis from density functional theory calculations[J]. Top Catal,2010,53:326−337. doi: 10.1007/s11244-010-9450-7
[87]	HAN Y F. Application of DFT modeling in Fischer-Tropsch synthesis over Co-based catalysts[J]. Chem Modell,2015,12:184.
[88]	YIN J, HE Y, LIU X, ZHOU X, HUO C F, GUO, WEN X D. Visiting CH₄ formation and C₁ + C₁ couplings to tune CH₄ selectivity on Fe surfaces[J]. J Catal,2019,372:217−225. doi: 10.1016/j.jcat.2019.03.007
[89]	马文平, 刘全生, 赵玉龙, 周敬来, 李永旺. 费托合成反应机理的研究进展[J]. 内蒙古工业大学学报(自然科学版),1999,(2):43−49. MA Wen-ping, LIU Quan-sheng, ZHAO Yu-long, ZHOU Jing-lai, LI Yong-wang. Research progress of Fischer-Tropsch synthesis reaction mechanism(science edition)[J]. J Inner Mongolia Univ Technol (Nat Sci Ed),1999,(2):43−49.
[90]	YAO Z, GUO C, MAO Y, HU, P. Quantitative determination of C-C coupling mechanisms and detailed analyses on the activity and selectivity for Fischer-Tropsch synthesis on Co(0001): Microkinetic modeling with coverage effects[J]. ACS Catal,2019,9(7):5957−5973. doi: 10.1021/acscatal.9b01150
[91]	LIU H, ZHANG R, LING L, WANG Q, WANG B, LI, D. Insight into the preferred formation mechanism of long-chain hydrocarbons in Fischer-Tropsch synthesis on Hcp Co (10-11) surfaces from DFT and microkinetic modeling[J]. Catal Sci Technol,2017,7(17):3758−3776.
[92]	WANG H, NIE X, CHEN Y, GUO X, SONG C. Facet effect on CO₂ adsorption, dissociation and hydrogenation over Fe catalysts: Insight from DFT[J]. J CO₂ Util,2018,26:160−170. doi: 10.1016/j.jcou.2018.05.003
[93]	CAO D B, LI Y W, WANG J, JIAO H. Chain growth mechanism of Fischer-Tropsch synthesis on Fe₅C₂(001)[J]. J Mol Catal A: Chem,2011,346(1/2):55−69. doi: 10.1016/j.molcata.2011.06.009
[94]	PETERSEN M A, VAN RENSBURG W J. CO dissociation at vacancy sites on Hägg iron carbide: Direct versus hydrogen-assisted routes investigated with DFT[J]. Top Catal, 2015, 58(10/11): 665–674.
[95]	ZHANG Q, KANG J, WANG Y. Development of novel catalysts for FischerT-ropsch synthesis: Tuning the product selectivity[J]. ChemCatChem,2010,2(9):1030−1058. doi: 10.1002/cctc.201000071
[96]	PAN X, JIAO F, MIAO D, BAO X. Oxide-zeolite-based composite catalyst concept that enables syngas chemistry beyond Fischer-Tropsch synthesis[J]. Chem Rev,2021,121(11):6588−6609. doi: 10.1021/acs.chemrev.0c01012
[97]	BILOEN P, HELLE J N, SACHTLER W M H. Incorporation of surface carbon into hydrocarbons during Fischer-Tropsch synthesis: Mechanistic implications[J]. J Catal,1979,58(1):95−107. doi: 10.1016/0021-9517(79)90248-3
[98]	PICHLER H, SCHULZ H. New insights in the area of the synthesis of hydrocarbons from CO and H₂[J]. Chem Ing Technol,1970,12(18):1160−1174.
[99]	GAUBE J, KLEIN H F. Further support for the two-mechanisms hypothesis of Fischer-Tropsch synthesis[J]. Appl Catal A: Gen, 2010, 374(1/2): 120–125.
[100]	LIU J, ZHANG A, LIU M, HU S, DING F, SONG C, GUO X. Fe-MOF-derived highly active catalysts for carbon dioxide hydrogenation to valuable hydrocarbons[J]. J CO₂ Util,2017,21:100−107. doi: 10.1016/j.jcou.2017.06.011
[101]	LU W, HERBIG M, LIEBSCHER C H, MORSDORF L, MARCEAU R K, DEHM G, RAABE D. Formation of eta carbide in ferrous martensite by room temperature aging[J]. Acta Mater,2018,158:297−312. doi: 10.1016/j.actamat.2018.07.071
[102]	WANG Y, LI Y, HUANG S, WANG J, WANG H, LV J, MA X. Insight into CH₄ formation and chain growth mechanism of Fischer-Tropsch synthesis on θ-Fe₃C (031)[J]. Chem Phys Lett,2017,682:115−121. doi: 10.1016/j.cplett.2017.06.006
[103]	TIAN X, WANG T, YANG Y, LI Y W, WANG J, JIAO H. Structures and energies of Cu clusters on Fe and Fe₃C surfaces from density functional theory computation[J]. Phys Chem Chem Phys,2014,16(48):26997−27011. doi: 10.1039/C4CP04012K
[104]	DUAN Y, SUN H, LU W. Theoretical study of CO adsorption and activation on h-Fe₇C₃(11-1) for Fischer-Tropsch synthesis[J]. Mol Catal,2022,532:112732. doi: 10.1016/j.mcat.2022.112732
[105]	CHUN H J, KIM Y T. Theoretical study of CO adsorption and activation on orthorhombic Fe₇C₃(001) surfaces for Fischer-Tropsch synthesis using density functional theory calculations[J]. Energies,2021,14(3):563. doi: 10.3390/en14030563
[106]	CHEN Y, MA L, ZHANG R, YE R, LIU W, WEI J, LIU J. Carbon-supported Fe catalysts with well-defined active sites for highly selective alcohol production from Fischer-Tropsch synthesis[J]. Appl Catal B: Environ,2022,312:121393. doi: 10.1016/j.apcatb.2022.121393
[107]	RIVERA DE LA CRUZ J G, SABBE M K, REYNIERS M F. First principle study on the adsorption of hydrocarbon chains involved in Fischer-Tropsch synthesis over iron carbides[J]. J Phys Chem C,2017,121(45):25052−25063. doi: 10.1021/acs.jpcc.7b05864
[108]	DENG C M, HUO C F, BAO L L, FENG G, LI Y W, WANG J, JIAO H. CO Adsorption on Fe₄C(100), (110), and (111) Surfaces in Fischer-Tropsch Synthesis[J]. J Phys Chem C,2008,112(48):19018−19029. doi: 10.1021/jp805702n
[109]	RAO K R P M, HUGGINS F E, MAHAJAN V, HUFFMAN G P, BUKUR D B, RAO V U S. Mössbauer study of CO-precipitated Fischer-Tropsch iron catalysts[J]. Hyperfine Interact,1994,93:1751−1754. doi: 10.1007/BF02072940
[110]	WANG H, NIE X, LIU Y, JANIK M J, HAN X, DENG Y, GUO X. Mechanistic insight into hydrocarbon synthesis via CO₂ hydrogenation on χ-Fe₅C₂ catalysts[J]. ACS Appl Mater Inter,2022,14(33):37637−37651. doi: 10.1021/acsami.2c07029
[111]	CAO J, SONG N, CHEN W, CAO Y, QIAN G, DUAN X, ZHOU X. Role of C-defective sites in CO adsorption over ϵ-Fe₂C and η-Fe₂C Fischer-Tropsch catalysts[J]. Chem Asian J,2020,15(23):4014−4022. doi: 10.1002/asia.202000995
[112]	CHEN B, WANG D, DUAN X, LIU W, LI Y, QIAN G, CHEN D. Charge-tuned CO activation over a χ-Fe₅C₂ Fischer-Tropsch catalyst[J]. ACS Catal,2018,8(4):2709−2714. doi: 10.1021/acscatal.7b04370
[113]	HENKELMAN G, ARNALDSSON A, JÓNSSON H. A fast and robust algorithm for Bader decomposition of charge density[J]. Comp Mater Sci,2006,36(3):354−360. doi: 10.1016/j.commatsci.2005.04.010
[114]	HE Y, ZHAO P, YIN J, GUO W, YANG Y, LI Y W, WEN X D. CO direct versus H-assisted dissociation on hydrogen coadsorbed χ-Fe₅C₂ Fischer-Tropsch catalysts[J]. J Phys Chem C,2018,122(36):20907−20917. doi: 10.1021/acs.jpcc.8b06988
[115]	SORESCU D C. Plane-wave density functional theory investigations of the adsorption and activation of CO on Fe₅C₂ surfaces[J]. J Phys Chem C,2009,113(21):9256−9274. doi: 10.1021/jp811381d
[116]	OZBEK M O, NIEMANTSVERDRIET J W H. Elementary reactions of CO and H₂ on C-terminated χ-Fe₅C₂(001) surfaces[J]. J Catal,2014,317:158−166. doi: 10.1016/j.jcat.2014.06.009
[117]	WEI J, SUN J, WEN Z, FANG C, GE Q, XU H. New insights into the effect of sodium on Fe₃O₄-based nanocatalysts for CO₂ hydrogenation to light olefins[J]. Catal Sci Technol,2016,6(13):4786−4793. doi: 10.1039/C6CY00160B
[118]	LIU W H, ZENG W, LIU F S, TANG B, LIU Q J, WANG W D. The mechanical and electronic properties of o-Fe₂C, h-Fe₃C, t-Fe₅C₂, m-Fe₅C₂ and h-Fe₇C₃ compounds: First-principles calculations[J]. Phys B Condens Matter,2021,606:412825. doi: 10.1016/j.physb.2021.412825
[119]	FARAOUN H I, ZHANG Y D, ESLING C, AOURAG H Crystalline, electronic, and magnetic structures of o-Fe₃C, χ-Fe₅C₂, and η-Fe₂C from first principle calculation[J]. J Appl Phys, 2006, 0512: 10.1063
[120]	BROOS R J, KLUMPERS B, ZIJLSTRA B, FILOT I A, HENSEN E J. A quantum-chemical study of the CO dissociation mechanism on low-index Miller planes of θ-Fe₃C[J]. Catal Today,2020,342:152−160. doi: 10.1016/j.cattod.2019.02.015
[121]	BRODEN G, GAFNER G, BONZEL H P. Co adsorption on potassium promoted Fe(110)[J]. Surf Sci,1979,84(2):295−314. doi: 10.1016/0039-6028(79)90139-0
[122]	PETERSEN M A, CARIEM M J, CLAEYS M, VAN STEEN E. A DFT perspective of potassium promotion of χ-Fe₅C₂ (100)[J]. Appl Catal A: Gen,2015,496:64−72. doi: 10.1016/j.apcata.2015.02.008
[123]	CAMERON S D, DWYER D J. Charge transfer effects on CO bond cleavage: CO and potassium on Fe (100)[J]. Surf Sci,1988,198(3):315−330. doi: 10.1016/0039-6028(88)90371-8
[124]	GRAF B, MUHLER M. The influence of the potassium promoter on the kinetics and thermodynamics of CO adsorption on a bulk iron catalyst applied in Fischer-Tropsch synthesis: A quantitative adsorption calorimetry, temperature-programmed desorption, and surface hydrogenation study[J]. Phys Chem Chem Phys,2011,13(9):3701−3710. doi: 10.1039/C0CP01875A
[125]	PHAM T H, QI Y, YANG J, DUAN X, QIAN G, ZHOU X, YUAN W. Insights into Hägg iron-carbide-catalyzed Fischer-Tropsch synthesis: Suppression of CH₄ formation and enhancement of C-C coupling on χ-Fe₅C₂ (510)[J]. ACS Catal,2015,5(4):2203−2208. doi: 10.1021/cs501668g
[126]	DENG L J, HUO C F, LIU X W, ZHAO X H, LI Y W, WANG J, JIAO H. Density functional theory study on surface C_xH_y formation from CO activation on Fe₃C(100)[J]. J Phys Chem C,2010,114(49):21585−21592. doi: 10.1021/jp108480e
[127]	HUO C F, LI Y W, WANG J, JIAO H. Insight into CH₄ formation in iron-catalyzed Fischer-Tropsch synthesis[J]. J Am Chem Soc,2009,131(41):14713−14721. doi: 10.1021/ja9021864
[128]	FAN H, SONG J, WANG Y, WANG Y, JIN Y, LIU S, LI T, LI Q, SHAO C, LIU W. Inhabiting inactive transition by coupling function of oxygen vacancies and Fe-C bonds achieving long cycle life of an iron-based anode[J]. Adv Mater,2023,2303360.
[129]	LI T, WEN X, LI Y W, JIAO H. Successive dissociation of CO, CH₄, C₂H₆, and CH₃CHO on Fe(110): Retrosynthetic understanding of FTS mechanism[J]. J Phys Chem C,2018,122(50):28846−28855. doi: 10.1021/acs.jpcc.8b10310
[130]	SCHWEICHER J, BUNDHOO A, KRUSE N. Hydrocarbon chain lengthening in catalytic CO hydrogenation: evidence for a CO-insertion mechanism[J]. J Am Chem Soc,2012,134(39):16135−16138.
[131]	YIN J, LIU X, LIU X W, WANG H, WAN H, WANG S, WEN X D. Theoretical exploration of intrinsic facet-dependent CH₄ and C₂ formation on Fe₅C₂ particle[J]. Appl Catal B: Environ,2020,278:119308. doi: 10.1016/j.apcatb.2020.119308
[132]	PHAM T H, CAO J, SONG N, CAO Y, CHEN B, QIAN G, DUAN X. Mechanistic aspects of facet-dependent CH₄/C_{2 +} selectivity over a χ-Fe₅C₂ Fischer-Tropsch catalyst[J]. Green Energy Environ, 2022, 7(3): 449–456.
[133]	YANG Y, YAN M F, ZHANG Y X, LI D Y, ZHANG C S, ZHU Y D, WANG Y X. Catalytic growth of diamond-like carbon on Fe₃C-containing carburized layer through a single-step plasma-assisted carburizing process[J]. Carbon,2017,122:1−8.
[134]	DE LA CRUZ J G R, SABBE M K, REYNIERS M F. First principle study of chain termination reactions during Fischer-Tropsch Synthesis on χ-Fe₅C₂(010)[J]. Mol Catal,2018,453:55−63. doi: 10.1016/j.mcat.2018.04.032
[135]	VAN SANTEN R A, MARKVOORT A J. Chain growth by CO insertion in the Fischer-Tropsch reaction[J]. ChemCatChem,2013,5(11):3384−3397.
[136]	KLEIS J, GREELEY J, ROMERO N A, MOROZOV V A, FALSIG H, LARSEN A H, JACOBSEN K W. Finite size effects in chemical bonding: From small clusters to solids[J]. Catal Lett,2011,141:1067−1071. doi: 10.1007/s10562-011-0632-0
[137]	LIU J X, WANG P, XU W, HENSEN E. Particle size and crystal phase effects in Fischer-Tropsch catalysts[J]. Eng Proc,2017,3(4):467−476.
[138]	MABASO E I, VAN STEEN E, CLAEYS M. Fischer-Tropsch synthesis on supported iron crystallites of different size[J]. Dgmk Tagungsbericht, 2006, (4): 93−100..
[139]	PARK J Y, LEE Y J, KHANNA P K, JUN K W, BAE J W, KIM Y. H. Alumina-supported iron oxide nanoparticles as Fischer-Tropsch catalysts: Effect of particle size of iron oxide[J]. J Mol Catal A: Chem,2010,323(1/2):84−90. doi: 10.1016/j.molcata.2010.03.025
[140]	LV Z Q, SUN S H, JIANG P, WANG B Z, FU W T. First-principles study on the structural stability, electronic and magnetic properties of Fe₂C[J]. Comput Mater Sci,2008,42(4):692−697. doi: 10.1016/j.commatsci.2007.10.007
[141]	ZHAO S, LIU X W, HUO C F, LI Y W, WANG J, JIAO H. Determining surface structure and stability of ε-Fe₂C, χ-Fe₅C₂, θ-Fe₃C and Fe₄C phases under carburization environment from combined DFT and atomistic thermodynamic studies[J]. Catal Struct React,2015,1(1):44−60.
[142]	ZHAO S, LIU X W, HUO C F, LI Y W, WANG J, JIAO H. Surface morphology of Hägg iron carbide (χ-Fe₅C₂) from ab initio atomistic thermodynamics[J]. J Catal,2012,294:47−53. doi: 10.1016/j.jcat.2012.07.003
[143]	LIANG B, DUAN H, SUN T, MA J, LIU X, XU J, ZHANG T. Effect of Na promoter on Fe-based catalyst for CO₂ hydrogenation to alkenes[J]. ACS Sustainable Chem Eng,2018,7(1):925−932.
[144]	WAN H J, WU B S, ZHANG C H, XIANG H W, LI Y W, XU B F, YI F. Study on Fe-Al₂O₃ interaction over precipitated iron catalyst for Fischer-Tropsch synthesis[J]. Catal Commun,2007,8(10):1538−1545. doi: 10.1016/j.catcom.2007.01.002
[145]	XU Y, SHI C, LIU B, WANG T, ZHENG J, LI W, LIU X. Selective production of aromatics from CO₂[J]. Catal Sci Technol,2019,9(3):593−610. doi: 10.1039/C8CY02024H
[146]	BLIGAARD T, NøRSKOV J K, DAHL S, MATTHIESEN J, CHRISTENSEN C H, SEHESTED J. The Brønsted-Evans-Polanyi relation and the volcano curve in heterogeneous catalysis[J]. J Catal,2004,224(1):206−217. doi: 10.1016/j.jcat.2004.02.034
[147]	AI X, XIE H, CHEN S, ZHANG G, XU B, ZHOU G. Highly dispersed mesoporous Cu/γ-Al₂O₃ catalyst for RWGS reaction[J]. Int J Hydrogen Energy,2022,47(33):14884−14895. doi: 10.1016/j.ijhydene.2022.03.002
[148]	GRZYBEK T, KLINIK J, PAPP H, BAERNS M. Characterization of Cu and K containing Fe/Mn oxide catalysts for Fischer-Tropsch synthesis[J]. Chem Eng Technol,1990,13(1):156−161. doi: 10.1002/ceat.270130122
[149]	KUMAR K L, NAIDU B N, SAINI H, GHOSH K, PRASAD V V D N, MONDAL P. Insights of precursor phase transition of (Cu-Zn-Al)/γ-Al₂O₃ hybrid catalyst for one step dimethyl ether synthesis from syngas[J]. Catal Today,2022,404:169−181. doi: 10.1016/j.cattod.2022.03.018
[150]	TIAN X, WANG T, YANG Y, LI Y W, WANG J, JIAO H. Surface morphology of Cu adsorption on different terminations of the Hägg iron carbide (χ-Fe₅C₂) Phase[J]. J Phys Chem C,2015,119(13):7371−7385. doi: 10.1021/acs.jpcc.5b01324
[151]	TIAN X, WANG T, YANG Y, LI Y W, WANG J, JIAO H. Copper promotion in CO adsorption and dissociation on the Fe(100) surface[J]. J Phys Chem C,2014,118(35):20472−20480. doi: 10.1021/jp506794w
[152]	TIAN X, WANG T, YANG Y, LIU G, TSANG S C E. Selective C₂⁺ alcohol synthesis from direct CO₂ hydrogenation over a Cs-promoted Cu-Fe-Zn catalyst[J]. ACS Catal,2020,10(9):5250−5260. doi: 10.1021/acscatal.0c01184
[153]	ATHARIBOROUJENY M, RAUB A, IABLOKOV V, CHENAKIN S, KOVARIK L, KRUSE N. Competing mechanisms in CO hydrogenation over Co-MnO_x catalysts[J]. ACS Catal,2019,9(6):5603−5612. doi: 10.1021/acscatal.9b00967
[154]	LIU X, XU M, CAO C, YANG Z, XU J. Effects of zinc on χ-Fe₅C₂ for carbon dioxide hydrogenation to olefins: Insights from experimental and density function theory calculations[J]. Chin J Chem Eng,2023,54:206−214. doi: 10.1016/j.cjche.2022.03.027
[155]	KHODAEI M, ENAYATI M H, KARIMZADEH F. Mechanochemical behavior of Fe₂O₃-Al-Fe powder mixtures to produce Fe₃Al-Al₂O₃ nanocomposite powder[J]. J mater Sci,2008,43:132−138. doi: 10.1007/s10853-007-2123-7
[156]	HUANG B, ISHIHARA K N, SHINGU P H. Metastable phases of Al-Fe system by mechanical alloying[J]. MSEA, 1997, 231(1/2): 72–79.
[157]	PIJOLAT M, PERRICHON V, BUSSIERE P. Study of the carburization of an iron catalyst during the Fischer-Tropsch synthesis: Influence on its catalytic activity[J]. J Catal,1987,107(1):82−91. doi: 10.1016/0021-9517(87)90274-0
[158]	ORDOMSKY V V, LEGRAS B, CHENG K, PAUL S, KHODAKOV A Y. The role of carbon atoms of supported iron carbides in Fischer-Tropsch synthesis[J]. Catal Sci Technol,2015,5(3):1433−1437. doi: 10.1039/C4CY01631A
[159]	ZHANG H, SONG X, ZHAO C, HU D, ZHANG W, JIA M. N-doped porous carbon-Fe_xC nanoparticle composites as catalysts for Friedel-Crafts acylation[J]. ACS Appl Nano Mater,2020,3(7):6664−6674. doi: 10.1021/acsanm.0c01107
[160]	TORRES GALVIS H M, BITTER J H, KHARE C B, RUITENBEEK M, DUGULAN A I, DE JONG K P. Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J]. Science,2012,335(6070):835−838. doi: 10.1126/science.1215614
[161]	SCHULTE H J, GRAF B, XIA W, MUHLER M. Nitrogen-and oxygen-functionalized multiwalled carbon nanotubes used as support in iron-catalyzed, high-temperature Fischer-Tropsch synthesis[J]. ChemCatChem,2012,4(3):350−355. doi: 10.1002/cctc.201100275
[162]	XIONG H, MOTCHELAHO M A, MOYO M, JEWELL L L, COVILLE N J. Fischer-Tropsch synthesis: Iron-based catalysts supported on nitrogen-doped carbon nanotubes synthesized by post-doping[J]. Appl Catal A: Gen,2014,482:377−386. doi: 10.1016/j.apcata.2014.06.019
[163]	WANG F, WANG Y, HAN K, YU H. Efficient elimination of formaldehyde over Pt/Fe₃O₄ catalyst at room temperature[J]. J Environ Chem Eng,2020,8(4):104041.
[164]	KOVALCHUK V I, KUZNETSOV B N. Hydrocarbon synthesis from CO and H₂ on (Fe + Pt) SiO₂ catalysts[J]. J Mol Catal A: Chem,1995,102(2):103−110. doi: 10.1016/1381-1169(95)90045-4
[165]	LI S, KRISHNAMOORTHY S, LI A, MEITZNER G D, IGLESIA E. Promoted iron-based catalysts for the Fischer-Tropsch synthesis: Design, synthesis, site densities, and catalytic properties[J]. J Catal,2002,206(2):202−217. doi: 10.1006/jcat.2001.3506
[166]	HE Y, ZHAO P, GUO W, YANG Y, HUO C F, LI Y W, WEN X D. Hägg carbide surfaces induced Pt morphological changes: A theoretical insight[J]. Catal Sci Technol,2016,6(17):6726−6738. doi: 10.1039/C6CY00764C
[167]	LU Y, CAO B, YU F, LIU J, BAO Z, GAO J. High selectivity higher alcohols synthesis from syngas over three-dimensionally ordered macroporous Cu-Fe catalysts[J]. ChemCatChem,2014,6(2):473−478. doi: 10.1002/cctc.201300749
[168]	ZHAO S, LIU X W, HUO C F, LI Y W, WANG J, JIAO H. The role of potassium promoter in surface carbon hydrogenation on Hägg carbide surfaces[J]. Appl Catal A: Gen,2015,493:68−76. doi: 10.1016/j.apcata.2015.01.006
[169]	ZHAO S, LIU X W, HUO C F, LI Y W, WANG J, JIAO H. Potassium promotion on CO hydrogenation on the χ-Fe₅C₂(111) surface with carbon vacancy[J]. Appl Catal A: Gen,2017,534:22−29. doi: 10.1016/j.apcata.2017.01.012
[170]	ZHAO S, LIU X W, HUO C F, WEN X D, GUO W, CAO D, JIAO H. Morphology control of K₂O promoter on Hägg carbide (χ-Fe₅C₂) under Fischer–Tropsch synthesis condition[J]. Catal Today,2016,261:93−100. doi: 10.1016/j.cattod.2015.07.035
[171]	ZHAO S, LIU X W, HUO C F, WEN X D, GUO W, CAO D, JIAO H. Highly activated K-doped iron carbide nanocatalysts designed by computational simulation for Fischer-Tropsch synthesis[J]. J Mater Chem A,2014,2(35):14371−14379. doi: 10.1039/C4TA02413C
[172]	HE Y, ZHAO P, LIU J, GUO W, YANG Y, LI Y W, WEN X D. Suppression by Pt of CO adsorption and dissociation and methane formation on Fe₅C₂(100) surfaces[J]. Phys Chem Chem Phys,2018,20(39):25246−25255. doi: 10.1039/C8CP04670K