Mechanistic insights and the role of spatial confinement in catalytic dimethyl ether carbonylation over SSZ-13 zeolite

doi:10.1016/S1872-2067(24)60040-9

Abstract

Abstract:

The SSZ-13 zeolite, which exhibits typical CHA topology characterized by 8-membered ring (8-MR) channels, has shown potential for catalyzing dimethyl ether (DME) carbonylation. However, current studies have yet to provide a comprehensive analysis of its catalytic mechanisms. In this study, we investigated the mechanism of SSZ-13-catalyzed DME carbonylation and the role of spatial confinement in this reaction. By exploiting the differences in the radii of the metal ions, we selectively replaced Brønsted acid sites (BAS) within specific channels, as confirmed by quantitative acidity analysis. Combining the activity data and the dissociation energies of the reactants on the BAS within different rings, we found that both the main and side reactions of DME carbonylation occurred on the 8-MR BAS of SSZ-13. Furthermore, the exchange of ions of different radii highlighted the confinement effect of the pore space in the SSZ-13 zeolite. Characterization of the deposits in spent catalysts, along with theoretical insights, revealed that the reduced cage space adversely affects the stabilization of side reaction intermediates, which in turn mitigates side reactions and improves the selectivity toward methyl acetate. This study presents an effective approach to modulate the acid site distribution and spatial confinement and provides critical insights into the determinants of the catalytic performance of SSZ-13. These findings offer valuable guidance for the future design and optimization of zeolites, aiming to enhance their efficacy in catalytic applications.

Key words: Dimethyl ether, Carbonylation, SSZ-13, Acid site, Spatial confinement

Xiaomin Zhang, Kai Cai, Ying Li, Ji Qi, Yue Wang, Yunduo Liu, Mei-Yan Wang, Shouying Huang, Xinbin Ma. Mechanistic insights and the role of spatial confinement in catalytic dimethyl ether carbonylation over SSZ-13 zeolite[J]. Chinese Journal of Catalysis, 2024, 61: 301-311.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60040-9

https://www.cjcatal.com/EN/Y2024/V61/I6/301

Figures/Tables 13

Fig. 1. XRD patterns of xM/H-SSZ-13 samples.

Fig. 2. SEM images of xM/H-SSZ-13 samples.

Table 1 Composition and acidic properties of the xM/H-SSZ-13 sample.

Sample	Si/Al^a	B acid amount (µmol g^‒1)
Sample	Si/Al^a	Total ^b	6-MR ^c	8-MR ^c
H-SSZ-13	14.4	565	214	351
3Na/H-SSZ-13	14.2	531	186	345
12Na/H-SSZ-13	14.3	501	161	340
25Na/H-SSZ-13	14.2	432	119	313
31Na/H-SSZ-13	14.4	377	106	271
3Cs/H-SSZ-13	14.3	516	195	321

Fig. 3. DME conversion (a,c) and MA selectivity (b,d) over H-SSZ-13, xNa/H-SSZ-13, and 3Cs/H-SSZ-13 samples. Reaction conditions: 473 K, 1.5 MPa, DME/CO = 1/49, 3000 h-1.

Fig. 4. NH3-TPD profiles (a) and FTIR spectra (b) of the O-H stretching region of samples with different Na and Cs loadings.

Fig. 5. Relationship between the space time yield of MA and the amount of 8-MR BAS over all samples. (For convenience, the sample name xM/H-SSZ-13 has been simplified to xM).

Fig. 6. Structure of the model with two H atoms and the relative energy of the model. (The energy of the A-O1-B-O4 model was used as a benchmark. Atom labels: pink: Al, yellow: Si, red: O; white: H).

Fig. 7. Location of the Na after ion exchange and relative energy of the model. (The energy of the model in which Na replaces the H atom in 6-MR and bonds with O2 and O3 atoms was used as a benchmark. Atom labels: pink: Al, yellow: Si, red: O; white: H; purple: Na).

Fig. 8. Relative energy profiles of the DME dissociation step on BAS within 6-MR and 8-MR.

Table 2 Pore structure information of the xM/H-SSZ-13 samples.

Sample	Surface area (m² g^‒1)			Pore volume (cm³ g^‒1)
Sample	BET	Micropore	External	Total	Micropore	Mesopore
SSZ-13	816.3	801.3	15.0	0.329	0.299	0.030
3Na/H-SSZ-13	763.7	756.5	7.2	0.303	0.283	0.020
12Na/H-SSZ-13	739.4	723.8	15.6	0.307	0.271	0.036
25Na/H-SSZ-13	691.6	682.8	8.8	0.282	0.256	0.026
31Na/H-SSZ-13	671.7	652.2	19.5	0.286	0.247	0.038
3Cs/H-SSZ-13	740.4	729.3	11.1	0.307	0.276	0.038

Fig. 9. Structures for the reactant, transition state, and final product of the CO insertion step over Na/H-SSZ-13 (a) and Cs/H-SSZ-13 (b). (c) Reaction barrier of CO insertion step in three different confining environments. (Atom labels: pink: Al, yellow: Si, red: O, white: H, purple: Na, dark purple: Cs).

Fig. 10. TG (a) and GC-MS (b) analysis curves of the used samples

Fig. 11. Adsorption energy of the side reaction intermediate (heptaMB+) over Na/H-SSZ-13, and Cs/H-SSZ-13 models. (Atom labels: pink: Al, yellow: Si, red: O, white: H, purple: Na, dark purple: Cs).

References

[1]	J. Goldemberg, Science, 2007, 315, 808-810.
[2]	V. Subramani, S. K. Gangwal, Energy Fuels, 2008, 22, 814-839.
[3]	D. Anđelković, B. Antić, M. Vujanić, M. Subotić, L. Radovanović, Energy Sources B, 2017, 12, 749-758.
[4]	X. Li, X. San, Y. Zhang, T. Ichii, M. Meng, Y. Tan, N. Tsubaki, ChemSusChem, 2010, 3, 1192-1199.
[5]	G. Yang, X. San, N. Jiang, Y. Tanaka, X. Li, Q. Jin, K. Tao, F. Meng, N. Tsubaki, Catal. Today, 2011, 164, 425-428.
[6]	D. Wang, G. Yang, Q. Ma, Y. Yoneyama, Y. Tan, Y. Han, N. Tsubaki, Fuel, 2013, 109, 54-60.
[7]	X. Gao, B. Xu, G. Yang, X. Feng, Y. Yoneyama, U. Taka, N. Tsubaki, Catal. Sci. Technol., 2018, 8, 2087-2097.
[8]	H. Zhan, S. Huang, Y. Li, J. Lv, S. Wang, X. Ma, Catal. Sci. Technol., 2015, 5, 4378-4389.
[9]	J. H. L. Mingting Xu, D. Wayne Goodman, Alak Bhattacharyya, Appl. Catal. A, 1997, 149, 289-301.
[10]	A. Bhan, A. D. Allian, G. J. Sunley, D. J. Law, E. Iglesia, J. Am. Chem. Soc., 2007, 129, 4919-4924.
[11]	P. Cheung, A. Bhan, G. J. Sunley, D. J. Law, E. Iglesia, J. Catal., 2007, 245, 110-123.
[12]	P. Cheung, A. Bhan, G. J. Sunley, E. Iglesia, Angew. Chem. Int. Ed., 2006, 45, 1617-1620.
[13]	M. Boronat, C. Martínez-Sánchez, D. Law, A. Corma, J. Am. Chem. Soc., 2008, 130, 16316-16323.
[14]	J. Liu, H. Xue, X. Huang, Y. Li, W. Shen, Catal. Lett., 2010, 139, 33-37.
[15]	S. Y. Park, C.-H. Shin, J. W. Bae, Catal. Commun., 2016, 75, 28-31.
[16]	X. Feng, J. Yao, H. Li, Y. Fang, Y. Yoneyama, G. Yang, N. Tsubaki, Chem. Commun., 2019, 55, 1048-1051.
[17]	J. R. Di Iorio, C. T. Nimlos, R. Gounder, ACS Catal., 2017, 7, 6663-6674.
[18]	X. Zhu, J. P. Hofmann, B. Mezari, N. Kosinov, L. Wu, Q. Qian, B. M. Weckhuysen, S. Asahina, J. Ruiz-Martínez, E. J. M. Hensen, ACS Catal., 2016, 6, 2163-2177.
[19]	F. Bleken, M. Bjørgen, L. Palumbo, S. Bordiga, S. Svelle, K.-P. Lillerud, U. Olsbye, Top. Catal., 2009, 52, 218-228.
[20]	L. Xie, F. Liu, L. Ren, X. Shi, F-S. Xiao, H. He, Environ. Sci. Technol., 2014, 48, 566-572.
[21]	L. Ren, L. Zhu, C. Yang, Y. Chen, Q. Sun, H. Zhang, C. Li, F. Nawaz, X. Meng, F-S. Xiao, Chem Commun., 2011, 47, 9789-9791.
[22]	J. Shang, G. Li, R. Singh, P. Xiao, J. Z. Liu, P. A. Webley, J. Phys. Chem. C, 2013, 117, 12841-12847.
[23]	Z. Li, J. Li, H. Rong, J. Zuo, X. Yang, Y. Xing, Y. Liu, G. Zhu, X. Zou, J. Am. Chem. Soc., 2022, 144, 6687-6691.
[24]	M. Lusardi, T. T. Chen, M. Kale, J. H. Kang, M. Neurock, M. E. Davis, ACS Catal., 2020, 10, 842-851.
[25]	S. Nystrom, A. Hoffman, D. Hibbitts, ACS Catal., 2018, 8, 7842-7860.
[26]	Z. Zhao, Y. Xing, S. Li, X. Meng, F-S. Xiao, R. McGuire, A.-N. Parvulescu, U. Müller, W. Zhang, J. Phys. Chem. C, 2018, 122, 9973-9979.
[27]	J. R. Di Iorio, S. Li, C. B. Jones, C. T. Nimlos, Y. Wang, E. Kunkes, V. Vattipalli, S. Prasad, A. Moini, W. F. Schneider, R. Gounder, J. Am. Chem. Soc., 2020, 142, 4807-4819.
[28]	M. Debost, P. B. Klar, N. Barrier, E. B. Clatworthy, J. Grand, F. Laine, P. Brazda, L. Palatinus, N. Nesterenko, P. Boullay, S. Mintova, Angew. Chem. Int. Ed., 2020, 59, 23491-23495.
[29]	X. Wang, N. Yan, M. Xie, P. Liu, P. Bai, H. Su, B. Wang, Y. Wang, L. Li, T. Cheng, P. Guo, W. Yan, J. Yu, Chem. Sci., 2021, 12, 8803-8810.
[30]	E. Duque-Redondo, K. Yamada, E. Masoero, J. Bañuelos Prieto, H. Manzano, Mater. Today Commun., 2023, 36, 106496.
[31]	M. Dahl, S. Kolboe, J. Catal., 1994, 149, 458-464.
[32]	M. Dahl, S. Kolboe, J. Catal., 1996, 161, 304-309.
[33]	S. Stian, O. Unni, J. Finn, B. Mortan, J. Phys. Chem. C, 2007, 111, 17981-17984.
[34]	S. Wang, Z. Qin, M. Dong, J. Wang, W. Fan, Chem Catal., 2022, 2, 1657-1685.
[35]	S. Muller, Y. Liu, F. M. Kirchberger, M. Tonigold, M. Sanchez-Sanchez, J. A. Lercher, J. Am. Chem. Soc., 2016, 138, 15994-16003.
[36]	Y. Chu, X. Yi, C. Li, X. Sun, A. Zheng, Chem. Sci., 2018, 9, 6470-6479.
[37]	A. Comas-Vives, M. Valla, C. Coperet, P. Sautet, ACS Cent. Sci., 2015, 1, 313-319.
[38]	A. T. Aguayo, A. G. Gayubo, R. Vivanco, M. Olazar, J. Bilbao, Appl. Catal. A, 2005, 283, 197-207.
[39]	M. A. Deimund, L. Harrison, J. D. Lunn, Y. Liu, A. Malek, R. Shayib, M. E. Davis, ACS Catal., 2016, 6, 542-550.
[40]	V. Babić, S. Koneti, S. Moldovan, N. Nesterenko, J.-P. Gilson, V. Valtchev, Microporous Mesoporous Mater., 2021, 314, 110863.
[41]	S. Bordiga, L. Regli, D. Cocina, C. Lamberti, M. Bjørgen, K. P. Lillerud, J. Phys. Chem. B, 2005, 109, 2779-2784.
[42]	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.
[43]	K. Suzuki, G. Sastre, N. Katada, M. Niwa, Phys. Chem. Chem. Phys, 2007, 9, 5980-5987.
[44]	J. Shang, G. Li, R. Singh, Q. Gu, K. M. Nairn, T. J. Bastow, N. Medhekar, C. M. Doherty, A. J. Hill, J. Z. Liu, P. A. Webley, J. Am. Chem. Soc., 2012, 134, 19246-19253.
[45]	W. Chen, G. Li, X. Yi, S. J. Day, K. A. Tarach, Z. Liu, S.-B. Liu, S. C. Edman Tsang, K. Góra-Marek, A. Zheng, J. Am. Chem. Soc., 2021, 143, 15440-15452.
[46]	D. B. Rasmussen, J. M. Christensen, B. Temel, F. Studt, P. G. Moses, J. Rossmeisl, A. Riisager, A. D. Jensen, Angew. Chem. Int. Ed., 2015, 54, 7261-7264.
[47]	L. Kilburn, M. DeLuca, A. J. Hoffman, S. Patel, D. Hibbitts, J. Catal., 2021, 400, 124-139.
[48]	X. Zhu, Y. Gao, M. Liu, Z. Yang, S. Li, H. Chen, B. Liu, W. Ma, E. J. M. Hensen, B. Shen, Microporous Mesoporous Mater., 2022, 345, 112260.
[49]	I. Yarulina, A. Dikhtiarenko, F. Kapteijn, J. Gascon, Catal. Sci. Technol., 2017, 7, 300-309.
[50]	J. Li, Y. Wei, J. Chen, S. Xu, P. Tian, X. Yang, B. Li, J. Wang, Z. Liu, ACS Catal., 2015, 5, 661-665.
[51]	S. Xu, A. Zheng, Y. Wei, J. Chen, J. Li, Y. Chu, M. Zhang, Q. Wang, Y. Zhou, J. Wang, F. Deng, Z. Liu, Angew. Chem. Int. Ed., 2013, 52, 11564-11568.
[52]	Y. Xue, J. Li, S. Wang, X. Cui, M. Dong, G. Wang, Z. Qin, J. Wang, W. Fan, J. Catal., 2018, 367, 315-325.