First-principles microkinetic simulations revealing the driving effect of zeolite in bifunctional catalysts for the conversion of syngas to olefins

doi:10.1016/S1872-2067(25)64682-1

Abstract

Abstract:

Direct conversion of syngas to light olefins (STO) on bifunctional catalysts has garnered significant attention, yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive. Herein, we theoretically addressed the kinetics of the direct STO reaction on typical ZnAl₂O₄/zeolite catalysts by establishing a complete reaction network, consisting of methanol synthesis and conversion, water gas shift (WGS) reaction, olefin hydrogenation, and other relevant steps. The WGS reaction occurs very readily on ZnAl₂O₄ surface whereas which is less active towards alkane formation via olefin hydrogenation, and the latter can be attributed to the characteristics of the H₂ heterolytic activation and the weak polarity of olefins. The driving effect of zeolite component towards CO conversion was demonstrated by microkinetic simulations, which is sensitive to reaction conditions like space velocity and reaction temperature. Under a fixed ratio of active sites between oxide and zeolite components, the concept of the “impossible trinity” of high CO conversion, high olefin selectivity, and high space velocity can thus be manifested. This work thus provides a comprehensive kinetic picture on the direct STO conversion, offering valuable insights for the design of each component of bifunctional catalysts and the optimization of reaction conditions.

Key words: Syngas to olefins, Bifunctional catalysis, Microkinetic simulations, Driving effect, Impossible trinity, ZnAl₂O₄ oxide

Wende Hu, Jun Ke, Yangdong Wang, Chuanming Wang. First-principles microkinetic simulations revealing the driving effect of zeolite in bifunctional catalysts for the conversion of syngas to olefins[J]. Chinese Journal of Catalysis, 2025, 73: 222-233.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64682-1

https://www.cjcatal.com/EN/Y2025/V73/I6/222

Figures/Tables 12

Scheme 1. Overview of the primary and secondary reactions in the direct conversion of syngas to light olefins on bifunctional catalysts consisting of oxide and zeolite components.

Scheme 2. Overview of the H2 activation to proton (Olat-H#) and hydride (Zn-H*), the key reactions of WGS, olefin hydrogenation to alkanes, and methanol conversion to methane/DME on ZnAl2O4(111) surface.

Fig. 1. Energy barriers and the corresponding transition state structures of the direct C-O bond scission of different CHxOHy intermediates on ZnAl2O4(111) surface.

Fig. 2. Energy profiles of the formation of methane from methanol (A) and ethane from ethene hydrogenation (B) via different reaction pathways on ZnAl2O4(111) surface at 0 K.

Fig. 3. Gibbs free energy profiles at 673 K and transition state structures of several key reactions on ZnAl2O4(111) surface.

Fig. 4. Activity dependences of some key reactions on temperature and total pressure on ZnAl2O4(111) surface in the absence of zeolite component.

Fig. 5. CO conversion and selectivity to methanol, DME, methane, CO2, olefin and alkane on ZnAl2O4-based bifunctional catalysts with respect to the activity of zeolite component for the conversion of methanol to olefins. Reaction conditions: 673 K, 3 MPa, CO/H2 = 1:2, Flow rate = 10 s-1. It is assumed that the contents of active sites on oxide and zeolite are the same (oxide:zeolite = 1:1).

Fig. 6. Dependence of the CO conversion on the flow rate of reactants and the zeolite activity (P = 3 MPa, A), and the total pressure and the zeolite activity (F = 10 s-1, B) on ZnAl2O4-based bifunctional catalysts. Reaction conditions: 673 K, CO/H2 = 1:2.

Fig. 7. Dependence of the selectivity on the flow rate of reactants and the zeolite activity (P = 3 MPa, A), and the total pressure and the zeolite activity (F = 10 s-1, B) on ZnAl2O4-based bifunctional catalysts. Reaction conditions: 673 K, CO/H2 = 1:2.

Fig. 8. CO conversion and selectivity to methanol, DME, methane, CO2, olefin and alkane on ZnAl2O4-based bifunctional catalysts (oxide:zeolite = 1:1) with respect to the activity of zeolite component for the conversion of methanol to olefins. Reaction conditions: 623 K (A) and 723 K (B), P = 3 MPa, CO/H2 = 1:2, Flow rate = 10 s-1.

Fig. 9. Dependence of the olefin/paraffin ratio on the flow rate of reactants and the zeolite activity (P = 3 MPa, A), and the total pressure and the zeolite activity (F = 10 s-1, B) on ZnAl2O4-based bifunctional catalysts. Reaction conditions: 673 K, CO/H2 = 1:2.

Fig. 10. Relation between the energy barrier of the Concerted hydrogenation and the charge difference of the atoms in the double bond of unsaturated molecules (0 K, A), and the charge density difference of the transition states of the Concerted hydrogenation of formaldehyde and ethene (the iso-surface value is 0.002 a-3, B) on ZnAl2O4(111) surface.

References

[1]	X. Pan, F. Jiao, D. Miao, X. Bao, Chem. Rev., 2021, 121, 6588-6609.
[2]	W. Zhou, K. Cheng, J. Kang, C. Zhou, V. Subramanian, Q. Zhang, Y. Wang, Chem. Soc. Rev., 2019, 48, 3193-3228.
[3]	S. Kasipandi, J. W. Bae, Adv. Mater., 2019, 31, 1803390.
[4]	F. Jiao, J. Li, X. Pan, J. Xiao, H. Li, H. Ma, M. Wei, Y. Pan, Z. Zhou, M. Li, S. Miao, J. Li, Y. Zhu, D. Xiao, T. He, J. Yang, F. Qi, Q. Fu, X. Bao, Science, 2016, 351, 1065-1068.
[5]	K. Cheng, B. Gu, X. Liu, J. Kang, Q. Zhang, Y. Wang, Angew. Chem. Int. Ed., 2016, 55, 4725-4728.
[6]	J. Su, H. Zhou, S. Liu, C. Wang, W. Jiao, Y. Wang, C. Liu, Y. Ye, L. Zhang, Y. Zhao, H. Liu, D. Wang, W. Yang, Z. Xie, M. He, Nat. Commun., 2019, 10, 1297.
[7]	F. Jiao, B. Bai, G. Li, X. Pan, Y. Ye, S. Qu, C. Xu, J. Xiao, Z. Jia, W. Liu, T. Peng, Y. Ding, C. Liu, J. Li, X. Bao, Science, 2023, 380, 727-730.
[8]	P. Tian, Y. Wei, M. Ye, Z. Liu, ACS Catal., 2015, 5, 1922-1938.
[9]	H. M. Torres Galvis, K. P. de Jong, ACS Catal., 2013, 3, 2130-2149.
[10]	L. Zhong, F. Yu, Y. An, Y. Zhao, Y. Sun, Z. Li, T. Lin, Y. Lin, X. Qi, Y. Dai, L. Gu, J. Hu, S. Jin, Q. Shen, H. Wang, Nature, 2016, 538, 84-87.
[11]	C.-M. Wang, Y.-D. Wang, Z.-K. Xie, Catal. Sci. Technol., 2016, 6, 6644-6649.
[12]	Y. Ni, Y. Liu, Z. Chen, M. Yang, H. Liu, Y. He, Y. Fu, W. Zhu, Z. Liu, ACS Catal., 2018, 9, 1026-1032.
[13]	W. Zhou, J. Kang, K. Cheng, S. He, J. Shi, C. Zhou, Q. Zhang, J. Chen, L. Peng, M. Chen, Y. Wang, Angew. Chem. Int. Ed., 2018, 57, 12012-12016.
[14]	A. V. Kirilin, J. F. Dewilde, V. Santos, A. Chojecki, K. Scieranka, A. Malek, Ind. Eng. Chem. Res., 2017, 56, 13392-13401.
[15]	K. Cheng, W. Zhou, J. Kang, S. He, S. Shi, Q. Zhang, Y. Pan, W. Wen, Y. Wang, Chem, 2017, 3, 334-347.
[16]	G. Raveendra, C. Li, B. Liu, Y. Cheng, F. Meng, Z. Li, Catal. Sci. Technol., 2018, 8, 3527-3538.
[17]	D. L. S. Nieskens, J. D. Lunn, A. Malek, ACS Catal., 2018, 9, 691-700.
[18]	Z. Liu, Y. Ni, X. Fang, W. Zhu, Z. Liu,, J. Energy Chem., 2021, 58, 573-576.
[19]	N. Li, Y. Zhu, F. Jiao, X. Pan, Q. Jiang, J. Cai, Y. Li, W. Tong, C. Xu, S. Qu, B. Bai, D. Miao, Z. Liu, X. Bao, Nat. Commun., 2022, 13, 2472.
[20]	C. Liu, J. Su, Y. Xiao, J. Zhou, S. Liu, H. Zhou, Y. Ye, Y. Lu, Y. Zhang, W. Jiao, L. Zhang, Y. Wang, C. Wang, X. Zheng, Z. Xie, Chem Catal., 2021, 1, 896-907.
[21]	J. Su, C. Liu, S. Liu, Y. Ye, Y. Du, H. Zhou, S. Liu, W. Jiao, L. Zhang, C. Wang, Y. Wang, Z. Xie, Cell Rep. Phys. Sci., 2021, 2, 100290.
[22]	J. Su, L. Zhang, H. Zhou, Y. Ye, X. Zheng, C. Liu, S. Liu, W. Jiao, X. Liu, C. Wang, Y. Wang, Z. Xie, ACS Catal., 2023, 13, 2472-2481.
[23]	M. Wang, Y. Han, S. Liu, Z. Liu, D. An, Z. Zhang, K. Cheng, Q. Zhang, Y. Wang, Chin. J. Catal., 2021, 42, 2197-2205.
[24]	Y. Ling, Y. Ran, W. Shao, N. Li, F. Jiao, X. Pan, Q. Fu, Z. Liu, F. Yang, X. Bao, Chin. J. Catal., 2022, 43, 2017-2025.
[25]	X. Liu, W. Zhou, Y. Yang, K. Cheng, J. Kang, L. Zhang, G. Zhang, X. Min, Q. Zhang, Y. Wang, Chem. Sci., 2018, 9, 4708-4718.
[26]	S. Ma, S.-D. Huang, Z.-P. Liu, Nat. Catal., 2019, 2, 671-677.
[27]	Z. Lai, N. Sun, J. Jin, J. Chen, H. Wang, P. Hu, ACS Catal., 2021, 12977-12988.
[28]	X. Fu, J. Li, J. Long, C. Guo, J. Xiao, ACS Catal., 2021, 11, 12264-12273.
[29]	Z. Chen, Y. Ni, F. Wen, Z. Zhou, W. Zhu, Z. Liu, Chin. J. Catal., 2021, 42, 835-843.
[30]	W.-D. Hu, C.-M. Wang, Y.-D. Wang, J. Ke, G. Yang, Y.-J. Du, W.-M. Yang, Appl. Surf. Sci., 2021, 569, 151064.
[31]	W.-D. Hu, J. Ke, Y.-D. Wang, C.-M. Wang, W.-M. Yang, Chin. J. Chem. Phys., 2022, 35, 655-663.
[32]	Y. Han, J. Xu, W. Xie, Z. Wang, P. Hu, ACS Catal., 2023, 13, 15074-15086.
[33]	Y. Han, J. Xu, W. Xie, Z. Wang, P. Hu, ACS Catal., 2023, 13, 5104-5113.
[34]	J. Ke, Y.-D. Wang, C.-M. Wang, Z.-K. Xie, Catal. Sci. Technol., 2024, 14, 3728-3738.
[35]	J. L. Weber, C. H. Mejía, K. P. de Jong, P. E. de Jongh, Catal. Sci. Technol., 2024, 14, 4799-4842.
[36]	Y. Ding, F. Jiao, X. Pan, Y. Ji, M. Li, R. Si, Y. Pan, G. Hou, X. Bao, ACS Catal., 2021, 11, 9729-9737.
[37]	Y. Wang, G. Wang, L. I. van der Wal, K. Cheng, Q. Zhang, K. P. de Jong, Y. Wang,, Angew. Chem. Int. Ed., 2021, 60, 17735-17743.
[38]	C.-M. Wang, W.-D. Hu, Y.-J. Du, G. Yang, J. Ke, Y.-L. Chen, Y.-D. Wang, Microporous Mesoporous Mater., 2024, 364, 112856.
[39]	U. Olsbye, S. Svelle, M. Bjørgen, P. Beato, T. V. W. Janssens, F. Joensen, S. Bordiga, K. P. Lillerud, Angew. Chem. Int. Ed., 2012, 51, 5810-5831.
[40]	V. Van Speybroeck, K. De Wispelaere, J. Van der Mynsbrugge, M. Vandichel, K. Hemelsoet, M. Waroquier, Chem. Soc. Rev., 2014, 43, 7326-7357.
[41]	C.-M. Wang, Y.-D. Wang, Z.-K. Xie, J. Catal., 2013, 301, 8-19.
[42]	C.-M. Wang, Y.-D. Wang, Z.-K. Xie, Chin. J. Catal., 2018, 39, 1272-1279.
[43]	J. Ke, W.-D. Hu, Y.-J. Du, Y.-D. Wang, C.-M. Wang, Z.-K. Xie, ACS Catal., 2023, 13, 8642-8661.
[44]	A. M. Bahmanpour, F. Héroguel, M. Kılıç, C. J. Baranowski, L. Artiglia, U. Röthlisberger, J. S. Luterbacher, O. Kröcher, ACS Catal., 2019, 9, 6243-6251.
[45]	S. Wang, P. Wang, D. Shi, S. He, L. Zhang, W. Yan, Z. Qin, J. Li, M. Dong, J. Wang, U. Olsbye, W. Fan, ACS Catal., 2020, 10, 2046-2059.
[46]	H. Song, D. Laudenschleger, J. J. Carey, H. Ruland, M. Nolan, M. Muhler, ACS Catal., 2017, 7, 7610-7622.
[47]	G. Li, F. Jiao, D. Miao, Y. Wang, X. Pan, T. Yokoi, X. Meng, F.-S. Xiao, A.-N. Parvulescu, U. Müller, X. Bao, J. Energy Chem., 2019, 36, 141-147.
[48]	V. P. Santos, G. Pollefeyt, D. F. Yancey, A. Ciftci Sandikci, B. Vanchura, D. L. S. Nieskens, M. de Kok-Kleiberg, A. Kirilin, A. Chojecki, A. Malek, J. Catal., 2020, 381, 108-120.
[49]	M. Wang, J. Kang, X. Xiong, F. Zhang, K. Cheng, Q. Zhang, Y. Wang, Catal. Today, 2021, 371, 85-92.
[50]	X. Han, D. Guo, Y. Wang, S. Huang, M.-Y. Wang, Y. Wang, M. Li, S. Wang, X. Ma, ACS Catal., 2024, 14, 9812-9828.
[51]	X. Liu, M. Wang, H. Yin, J. Hu, K. Cheng, J. Kang, Q. Zhang, Y. Wang, ACS Catal., 2020, 10, 8303-8314.
[52]	Q. Han, P. Gao, K. Chen, L. Liang, Z. Zhao, X. Yao, D. Xiao, X. Han, G. Hou, Chem, 2023, 9, 721-738.
[53]	A. Ye, Z. Li, J. Ding, W. Xiong, W. Huang, ACS Catal., 2021, 11, 10014-10019.
[54]	X. Zhang, G. Zhang, W. Liu, F. Yuan, J. Wang, J. Zhu, X. Jiang, A. Zhang, F. Ding, C. Song, X. Guo, Appl. Catal. B, 2021, 284, 119700.
[55]	M. Wang, L. Zheng, G. Wang, J. Cui, G.-L. Guan, Y.-T. Miao, J.-F. Wu, P. Gao, F. Yang, Y. Ling, X. Luo, Q. Zhang, G. Fu, K. Cheng, Y. Wang, J. Am. Chem. Soc., 2024, 146, 14528-14538.
[56]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[57]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[58]	S. Grimme, S. Ehrlich, L. Goerigk, J. Comput. Chem., 2011, 32, 1456-1465.
[59]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[60]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[61]	H. S. C. O'Neill, W. A. Dollase, Phys. Chem. Miner., 1994, 20, 541-555.
[62]	G. Henkelman, H. Jónsson, J. Chem. Phys., 1999, 111, 7010-7022.
[63]	Y. J. Du, W. D. Hu, C. M. Wang, J. Zhou, G. Yang, Y. D. Wang, W. M. Yang, Catal. Sci. Technol., 2021, 11, 2031-2046.
[64]	A. J. Medford, C. Shi, M. J. Hoffmann, A. C. Lausche, S. R. Fitzgibbon, T. Bligaard, J. K. Nørskov, Catal. Lett., 2015, 145, 794-807.
[65]	J. Chen, M. Jia, P. Hu, H. Wang, J. Comput. Chem., 2021, 42, 379-391.
[66]	C.-M. Wang, R. Y. Brogaard, B. M. Weckhuysen, J. K. Nørskov, F. Studt, J. Phys. Chem. Lett., 2014, 5, 1516-1521.
[67]	C.-M. Wang, Y.-D. Wang, Z.-K. Xie, Catal. Sci. Technol., 2019, 9, 2245-2252.
[68]	B. Bai, Y. Ye, F. Jiao, J. Xiao, Y. Pan, Z. Cai, M. Chen, X. Pan, X. Bao, J. Am. Chem. Soc., 2024, 146, 34909-34915.