CuFe (100)及(110)面上合成气制低碳醇碳链增长机理研究

王康明; 张海涛; 李涛

doi:10.14135/j.cnki.1006-3080.20210127003

CuFe (100)及(110)面上合成气制低碳醇碳链增长机理研究

doi: 10.14135/j.cnki.1006-3080.20210127003

华东理工大学大型工业反应器工程教育部工程研究中心，上海 200237

详细信息

作者简介:
王康明（1996—），男，安徽淮南人，硕士生，主要研究方向为催化反应工程。E-mail：1561409713@qq.com

通讯作者:
李　涛，E-mail：tli@ecust.edu.cn

中图分类号: TQ032.4
计量
- 文章访问数: 567
- HTML全文浏览量: 280
- PDF下载量: 158
- 被引次数: 0
出版历程
- 收稿日期: 2021-01-27
- 网络出版日期: 2021-04-12
- 刊出日期: 2022-04-22

Carbon Chain Growth Mechanism of Higher Alcohols Formation from Syngas on CuFe (100) and (110)

Engineering Research Center of the Large Scale Reactor Engineering and Technology, Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: CuFe混合催化剂是一种重要的合成气制低碳醇用催化剂。为深入了解合成气制低碳醇的反应机理，从量子尺度利用密度泛函理论（DFT）研究了CuFe混合催化剂两个主要表面(100)及(110)上的碳链增长机理。计算发现Cu在Fe (100)及Fe (110)面上倾向于单层聚集分布，CuFe (100)面上CO活化机理为H辅助CO生成CHO，随后逐步加氢生成CH₂O和CH₃O，CH₃O更倾向于生成CH₃OH，其碳链增长方式为CHO插入；CuFe (110)面上CO活化机理与(100)面上相同，H辅助CO加氢生成CHO，并不断加氢依次生成CH₂O和CH₃O，但CH₃O更倾向于生成CH₃，CH₃进一步与CO耦合完成碳链的增长。
- CuFe /
- 合成气 /
- 低碳醇 /
- 碳链增长 /
- DFT
Abstract: CuFe catalyst is an important catalyst for higher alcohols formation from syngas. In order to gain mechanistic insight into the reaction, spin-polarized density functional theory calculations were performed to investigate the growth mechanism of carbon chains on CuFe (100) and (110) surfaces. The calculated results show that Cu atoms prefer to aggregate rather than homogeneously disperse on the Fe (100) and (110) surfaces. With the increase of Cu atoms, the surface energy decreases gradually, suggesting that the surface tends to be more stable. The dominant activation mechanism of CO on CuFe (100) surfaces is ascribed to a H-assisted CO dissociation via CHO intermediate, which is then progressively hydrogenated to form CH₂O and CH₃O. Subsequently, CH₃O is dominantly hydrogenated to form CH₃OH. The pathway of carbon chain growth is found to be CHO rather than CO insertion. The activation mechanism of CO on CuFe (110) surface is found to be similar to that on CuFe (100) surface. The pathway of CH₃O formation is CO+3H→CHO+2H→CH₂O+H→CH₃O. On the CuFe (110) surface, CH₃ formation is more thermodynamically favorable than CH₃OH, which leads to the production of more CH₃ for CO insertion to form C₂₊ higher alcohols. This research offers mechanistic insight into improving the production of higher alcohols on CuFe catalyst.
- CuFe /
- syngas /
- higher alcohol /
- carbon chain growth /
- DFT

HTML全文

图 1 (a) Fe (100)及(b) Fe (110)表面Cu原子排布

Figure 1. Distribution of Cu atom on (a) Fe (100) and (b) Fe (110) surfaces

下载: 全尺寸图片幻灯片

图 2 (a) CuFe (100)与(b) CuFe (110)表面模型及其吸附位

Figure 2. Surface models and adsorption sites of (a) CuFe (100) and (b) CuFe (110)

下载: 全尺寸图片幻灯片

图 3 (a)CuFe (100)及(b)CuFe (110)面上所有物种最稳定吸附构型

Figure 3. Most stable adsorption configuration of species on (a) CuFe (100) and (b) CuFe (110) surfaces

下载: 全尺寸图片幻灯片

图 4 (a) CuFe (100)与(b) CuFe (110)面上CO活化解离过程涉及的反应势能图与过渡态构型

Figure 4. Potential energy diagram and transition state configuration of the involved reaction in the CO dissociation process on (a) CuFe (100) and (b) CuFe (110) surfaces

下载: 全尺寸图片幻灯片

图 5 (a)CuFe (110)及(b)CuFe (110)面上CH_x, CH_xO, CH_xOH物种形成过程涉及反应的势能图与过渡态构型

Figure 5. Potential energy diagram and transition state configuration of the involved reaction in CH_x, CH_xO, CH_xOH species on (a) CuFe (100) and (b) CuFe (110) surfaces

下载: 全尺寸图片幻灯片

图 6 (a) CuFe (100)与(b) CuFe (110)面上碳链增长过程涉及反应的势能图与过渡态构型

Figure 6. Potential energy diagram and transition state configuration of the involved reaction in carbon chain growth process on (a) CuFe (100) and (b) CuFe (110) surfaces

下载: 全尺寸图片幻灯片

表 1 Cu原子排布方式不同时Fe (100)和Fe (110)表面的表面能

Table 1. Surface energy on Fe (100) and Fe (110) surfaces with different Cu atom distribution methods

Fe (100)	E_surf/（J·m⁻²）	Fe (110)	E_surf/（J·m⁻²）
Cu0	6.32	Cu0	7.60
Cu4	5.91	Cu3	7.14
Cu4(2)	5.98	Cu3(2)	7.39
Cu8	5.61	Cu6	6.76
Cu8(2)	5.66	Cu6(2)	6.95
Cu12	5.18	Cu9	6.36
Cu12(2)	5.32	Cu9(2)	6.41
Cu16	4.98	Cu12	5.94

下载: 导出CSV

表 2 CuFe (100)及CuFe (110)面上所有物种的最稳定吸附位及吸附能

Table 2. Most stable adsorption sites and adsorption energies of species on CuFe (100) and CuFe (110) surfaces

Species	CuFe (100)			CuFe (110)
Species	Adsorption site	E_ads/eV	Bonding atom	Adsorption site	E_ads/eV	Bonding atom
C	Hollow	−7.50	C	LB	−9.07	C
O	Hollow	−6.10	O	LB	−6.23	O
H	Hollow	−2.88	H	TF	−5.28	H
CO	Hollow	−1.61	C	TF	−2.52	C
CHO	Bridge-Hollow-Bridge	−2.28	C,O	TF-LB-TF	−3.93	C,O
CH₂O	Hollow	−3.61	C,O	SB-TF-SB	−4.67	C,O
CH₃O	Hollow	−2.37	O	LB	−4.37	O
COH	Hollow	−3.82	C	LB	−5.09	C
CHOH	Bridge	−3.10	C	LB-TF	−4.06	C
CH₂OH	Top-Bridge-Top	−2.41	C,O	T-SB-T	−2.72	C,O
CH₃OH	Top-Hollow	−1.24	O	T-TF	−2.66	C
CH	Hollow	−6.58	C	LB	−6.78	C
CH₂	Hollow	−4.50	C	LB	−5.23	C
CH₃	Bridge	−2.20	C	TF	−3.72	C
CH₄	Top	−0.38	―	T	―	―
C₂H₆	Bridge-Top-Bridge	−0.13	―	TF-T-TF	―	―
CH₃CO	Top-Bridge-Top	−3.85	C,O	T-SB	−3.48	C,O
CH₃CHO	Top-Bridge	−3.58	O	T-SB	−4.16	O

下载: 导出CSV

参考文献(29)

[1]	XIAO K, BAO Z H, QI X Z, et al. Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J]. Chinese Journal of Catalysis, 2013, 34(1): 116-129. doi: 10.1016/S1872-2067(11)60496-8
[2]	CHENG J, HU P, ELLIS P, et al. A first-principles study of oxygenates on Co surfaces in Fischer-Tropsch synthesis[J]. Journal of Physical Chemistry C, 2008, 112(25): 9464-9473. doi: 10.1021/jp802242t
[3]	WANG J B, ZHANG X R, SUN Q, et al. Chain growth mechanism on bimetallic surfaces for higher alcohol synthesis from syngas[J]. Catalysis Communications, 2015, 61(61): 57-61.
[4]	NING X, AN Z, HE J. Remarkably efficient CoGa catalyst with uniformly dispersed and trapped structure for ethanol and higher alcohol synthesis from syngas[J]. Journal of Catalysis, 2016, 340: 236-247. doi: 10.1016/j.jcat.2016.05.014
[5]	士丽敏, 储伟, 刘增超. 合成气制低碳醇用催化剂的研究进展[J]. 化工进展, 2011, 30(1): 162-166.
[6]	苏艳敏, 郑化安, 付东升, 等. Cu-Fe基催化剂在煤基合成气制低碳混合醇中的应用[J]. 洁净煤技术, 2013, 19(5): 68-73.
[7]	SONG N, CAO J B, CHEN B X, et al. CO adsorption and activation of η-Fe₂C Fischer Tropsch catalyst[J]. Industrial & Engineering Chemistry Research, 2019, 58(47): 21296-21303.
[8]	WANG B J, LIANG D L, ZHANG R G, et al. Crystal facet dependence for the selectivity of C₂ species over Co₂C catalysts in the Fischer-Tropsch synthesis[J]. The Journal of Physical Chemistry C, 2018, 122(51): 29249-29258. doi: 10.1021/acs.jpcc.8b08783
[9]	SUN X Y, YU Y Z, ZHANG M H. Insight into the effect of promoter Co on C₂ oxygenate formation from syngas on CoCu (100) and Cu (100): A comparative DFT study[J]. Applied Surface Science, 2018, 434: 28-39. doi: 10.1016/j.apsusc.2017.10.164
[10]	WANG W, WANG Y, WANG G C. Ethanol synthesis from syngas over Cu(Pd)-doped Fe(100): A systematic theoretical investigation[J]. Physical Chemistry Chemical Physics, 2018, 20(4): 2492-2507. doi: 10.1039/C7CP06693G
[11]	ZHAO X H, LI Y W, WANG J G, et al. CO adsorption, CO dissociation, and C-C coupling on Cu monolayer-covered Fe (100)[J]. Journal of Fuel Chemistry and Technology, 2011, 39(12): 956-960. doi: 10.1016/S1872-5813(12)60004-8
[12]	TIAN X X, WANG T, YANG Y, et al. Structures and energies of Cu clusters on Fe and Fe₃C surfaces from density functional theory computation[J]. Physical Chemistry Chemical Physics, 2014, 16(48): 26997-27011. doi: 10.1039/C4CP04012K
[13]	ZHAO Y H, LI S G, SUN Y H. CO dissociation mechanism on Cu-doped Fe (100) surfaces[J]. Journal of Physical Chemistry C, 2017, 117(47): 24920-24931.
[14]	ZHAN J Y, ZHAN F Q, XU S Y, et al. DFT studies on doping effect of Al₁₂X: Adsorption and dissociation of H₂O on Al₁₂X clusters[J]. Journal of Physical Chemistry A, 2013, 117(10): 2213-2222. doi: 10.1021/jp309422p
[15]	LI J R, ZHANG R G, WANG B J. Influence of the hydroxylation of γ-Al₂O₃ surfaces on the stability and growth of Cu for Cu/γ-Al₂O₃ catalyst: A DFT study[J]. Applied Surface Science, 2013, 270: 728-736. doi: 10.1016/j.apsusc.2013.01.139
[16]	CHANG C R, WANG Y G, LI J. Theoretical investigations of the catalytic role of water in propene epoxidation on gold nanoclusters: A hydroperoxyl-mediated pathway[J]. Nano Research, 2011, 4(1): 131-142. doi: 10.1007/s12274-010-0083-8
[17]	JIANG Q G, AO Z M, CHU D W, et al. Reversible transition of graphene from hydrophobic to hydrophilic in the presence of an electric field[J]. The Journal of Physical Chemistry C, 2012, 116(36): 19321-19326. doi: 10.1021/jp3050466
[18]	AO Z M, PEETERS F M. Electric field activated hydrogen dissociative adsorption to nitrogen-doped graphene[J]. The Journal of Physical Chemistry C, 2010, 114(34): 14503-14509. doi: 10.1021/jp103835k
[19]	ZHANG R G, WANG G R, WANG B J. Insights into the mechanism of ethanol formation from syngas on Cu and an expanded prediction of improved Cu-based catalyst[J]. Journal of Catalysis, 2013, 305: 238-255. doi: 10.1016/j.jcat.2013.05.028
[20]	SUN Q, LI Z, SEARLES D J, et al. Charge-controlled switchable CO₂ capture on boron nitride nanomaterials[J]. Journal of the American Chemical Society, 2013, 135(22): 8246-8253. doi: 10.1021/ja400243r
[21]	YANG Y X, WHITE M G, LIU P. Theoretical study of methanol synthesis from CO₂ hydrogenation on metal-doped Cu(111) surfaces[J]. Journal of Physical Chemistry C, 2012, 116(1): 248-256. doi: 10.1021/jp208448c
[22]	LO J M H, ZIEGLER T. A first-principle study of chain propagation steps in the Fischer-Tropsch synthesis on Fe (100)[J]. The Journal of Physical Chemistry C, 2008, 112(35): 13681-13691. doi: 10.1021/jp802042s
[23]	YAMAGISHI S, FUJIMOTO T, YASUJI I Y, et al. Studies of CO adsorption on Pt (100), Pt (410) and Pt (110) surfaces using density functional theory[J]. Journal of Physical Chemistry B, 2005, 109(18): 8899-8908. doi: 10.1021/jp050722i
[24]	WANG W, WANG Y, WANG G C. CO dissociation mechanism on Pd-doped Fe (100): Comparison with Cu/Fe (100)[J]. The Journal of Physical Chemistry C, 2017, 121(12): 6820-6834. doi: 10.1021/acs.jpcc.7b00903
[25]	宋楠,陈炳旭,段学志,等. 黄托催化剂γ-Fe₂C (011)上CO吸附与活化行为[J]. 陕西师范大学学报(自然科学版), 2019, 47(1): 15-21.
[26]	MOHAMMAD R E, MANUEL P J, HANS N. Direct versus hydrogen-assisted CO dissociation on the Fe (100) surface: A DFT study[J]. Chemphyschem, 2012, 13(1): 89-91. doi: 10.1002/cphc.201100759
[27]	ZHENG H Y, ZHANG R G, LI Z, et al. Insight into the mechanism and possibility of ethanol formation from syngas on Cu (100) surface[J]. Molecular Catalysis, 2015, 404: 115-130.
[28]	林维明, 甘世凡, 黄传荣, 等. 在铜铁系催化剂上合成低碳醇的研究[J]. 天然气化工: C1化学与化工, 1987, 1: 14-19.
[29]	REN B H, DONG X Q, YU Y Z, et al. A density functional theory study on the carbon chain growth of ethanol formation on Cu-Co (111) and (211) surfaces[J]. Applied Surface Science, 2017, 412(1): 374-384.