K对Hägg碳化物逆水煤气变换反应作用的理论研究

doi:10.1016/S1872-2067(24)60278-0

摘要/Abstract

摘要： 钾(K)作为助剂可以提高铁基催化剂在逆水煤气变换(rWGS)反应中的催化性能, 这一特性与CO₂-H₂混合物的费托(FT)合成过程密切相关. 为了阐明K助剂的作用机理, 我们结合密度泛函理论(DFT)计算和微观动力学建模, 对Hägg碳化物(χ-Fe₅C₂)的两个代表性表面终端, 即(010)和(510)进行了研究. 结果表明, K₂O的存在增强了CO₂和H₂在Hägg碳化物上的吸附能力, 并通过提高靠近助剂氧化物的Fe原子的电子密度来促进吸附CO₂的C-O键解离. 此外, 表面Fe原子电子密度的的增加导致了与吸附CO₂的键合轨道的电子排斥效应增强. 微观动力学模拟预测, K₂O在CO₂-FT合成过程中提高了CO₂转化率. K₂O还增强了CO的吸附和解离, 促进了甲烷的形成, 甲烷在这里被用作CO₂-FT合成过程中碳氢化合物形成的典型代表. 在CO₂-FT反应体系中, CO解离和通过H₂O去除O作为速率控制步骤相互竞争.

关键词: 费托合成, H?gg碳化铁, 逆水煤气变换, 钾, 密度泛函理论

Abstract:

Potassium (K) is known to enhance the catalytic performance of Fe-based catalysts in the reverse water-gas shift (rWGS) reaction, which is highly relevant during Fischer-Tropsch (FT) synthesis of CO₂-H₂ mixtures. To elucidate the mechanistic role of K promoter, we employed density functional theory (DFT) calculations in conjunction with microkinetic modelling for two representative surface terminations of Hägg carbide (χ-Fe₅C₂), i.e., (010) and (510). K₂O results in stronger adsorption of CO₂ and H₂ on Hägg carbide and promotes C-O bond dissociation of adsorbed CO₂ by increasing the electron density on Fe atoms close to the promoter oxide. The increased electron density of the surface Fe atoms results in an increased electron-electron repulsion with bonding orbitals of adsorbed CO₂. Microkinetics simulations predict that K₂O increases the CO₂ conversion during CO₂-FT synthesis. K₂O also enhances CO adsorption and dissociation, facilitating the formation of methane, used here as a proxy for hydrocarbons formation during CO₂-FT synthesis. CO dissociation and O removal via H₂O compete as the rate-controlling steps in CO₂-FT.

Key words: Fischer-Tropsch synthesis, H?gg carbide, Reverse water-gas shift, Potassium, Density functional theory

任宪轩, Rozemarijn D. E. Krösschell, 门卓武, 王鹏, Ivo A. W. Filot, Emiel J. M. Hensen. K对Hägg碳化物逆水煤气变换反应作用的理论研究[J]. 催化学报, 2025, 72: 289-300.

Xianxuan Ren, Rozemarijn D. E. Krösschell, Zhuowu Men, Peng Wang, Ivo A. W. Filot, Emiel J. M. Hensen. A theoretical study of the role of K on the reverse water-gas shift reaction on Hägg carbide[J]. Chinese Journal of Catalysis, 2025, 72: 289-300.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60278-0

https://www.cjcatal.com/CN/Y2025/V72/I5/289

图/表 11

Fig. 1. Top and side view of the (010) (a) and the (510) (b) surfaces models of Ha?gg carbide. The solid lines correspond to the top and bottom edges of the periodic supercell. The FR and P5 sites are indicated by dotted white lines.

Fig. 2. Reaction energy diagrams of the formation of KOH, K2O and K2CO3 on the (010) surface (a) and the (510) surface (b) of χ-Fe5C2.

Fig. 3. The most stable adsorption configurations of CO2 and H on the (top row) unpromoted and (bottom row) K2O-promoted (010) and (510) surfaces.

Table 1 Forward reaction barriers (Ef), backward reaction barriers (Eb) and reaction energies (Erxn) of CO dissociation via direct and H-assisted pathways, along with the difference in forward barrier (ΔEf) between the unpromoted and promoted surfaces for the (010) and (510) of χ-Fe5C2.

Surface	Elementary step	Unpromoted			K₂O Promoted
Surface	Elementary step	E_f (kJ/mol)	E_b (kJ/mol)	E_rxn (kJ/mol)	E_f (kJ/mol)	E_b (kJ/mol)	E_rxn (kJ/mol)	ΔE_f (kJ/mol)
(010)	CO₂* + * → CO* + O*	56	142	-86	45	146	-101	-11
(010)	CO₂* + H* → HCOO* + *	103	23	80	63	9	54	-40
(010)	CO₂* + H* → COOH* + *	122	44	78	118	32	86	-4
(010)	HCOO* + * → HCO* + O*	28	136	-108	64	133	-69	36
(010)	COOH* + * → CO* + OH*	34	115	-81	36	168	-132	2
(510)	CO₂* + * → CO* + O*	33	171	-138	14	156	-142	-19
(510)	CO₂* + H* → HCOO* + *	79	25	54	71	3	68	-8
(510)	CO₂* + H* → COOH* + *	57	4	53	115	61	54	58
(510)	HCOO* + * → HCO* + O*	55	115	-60	26	113	-87	-29
(510)	COOH* + * → CO* + OH*	68	171	-103	70	153	-83	2

Fig. 4. DOS of C-O bond of CO2 in the gas phase (a) and on the (010) surface (b), and on the K2O-promoted (010) surface (c) of χ-Fe5C2. COHP of the C-O bonds in CO2 in the gas phase (d), on the (010) surface (e), and on the K2O-promoted (010) surface (f) of χ-Fe5C2.

Fig. 5. iDOS (a,b) and iCOHP (c,d) of C-O bond of CO2 in the gas phase, on the unpromoted surfaces; and the K2O-promoted surfaces. The results for the unpromoted and K2O-promoted surfaces are indicated by hashed and dotted bars, respectively.

Fig. 6. Reaction energy diagrams of H2O formation through O* hydrogenation followed by OH* hydrogenation or OH* disproportionation pathways on the (510) (a) and K2O-promoted (510) (b) surfaces of χ-Fe5C2.

Fig. 7. Reaction energy diagrams of CH4 formation starting from gaseous CO and H2 on the unpromoted and K2O-promoted (510) surfaces of χ-Fe5C2.

Fig. 8. Microkinetics simulations on the unpromoted and K2O-promoted (510) surfaces of χ-Fe5C2: CO2 conversion rate (a) and CO and CH4 rates (b) as a function of temperature (p = 20 bar, H2/CO ratio = 4).

Fig. 9. Microkinetics simulations on the (left) unpromoted and (right) K2O-promoted (510) surfaces of χ-Fe5C2: selectivity (a,b) and coverage (c,d) as a function of temperature (p = 20 bar, H2/CO ratio = 4).

Fig. 10. Microkinetics simulations on the (left) unpromoted and (right) K2O-promoted (510) surfaces of χ-Fe5C2: degree of rate control (a,b) and reaction order and apparent activation energy (c,d) as a function of temperature (p = 20 bar, H2/CO ratio = 4).

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