Citation: Li Shihan, Zhao Zhenchao, Li Shikun, Xing Youdong, Zhang Weiping. Aluminum Distribution and Brønsted Acidity of Al-Rich SSZ-13 Zeolite: A Combined DFT Calculation and Solid-State NMR Study[J]. Acta Physico-Chimica Sinica, ;2020, 36(4): 190302. doi: 10.3866/PKU.WHXB201903021 shu

Aluminum Distribution and Brønsted Acidity of Al-Rich SSZ-13 Zeolite: A Combined DFT Calculation and Solid-State NMR Study

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, P. R. China

Corresponding author: Zhang Weiping, wpzhang@dlut.edu.cn
Received Date: 11 March 2019
Revised Date: 11 April 2019
Accepted Date: 11 April 2019
Available Online: 18 April 2019
Fund Project: the National Natural Science Foundation of China 21603022the Fundamental Research Funds for the Central Universities in China DUT17TD04the National Natural Science Foundation of China 21872017The project was supported by the National Natural Science Foundation of China (21872017, 21603022), the Fundamental Research Funds for the Central Universities in China (DUT17TD04) and the Supercomputing Center of Dalian University of Technology, China

SSZ-13 zeolite with a chabazite (CHA) topology structure has important applications for methanol to olefin (MTO) conversion and selective catalytic reduction of nitrogen oxides (NO_x) by ammonia (NH₃-SCR) to reduce diesel engine exhaust emissions. It has been reported that the Al-rich SSZ-13 zeolite can be used to tune the selectivity of olefins in the MTO reaction, and significantly enhance NO conversions at lower temperatures in NH₃-SCR. Thus, the aluminum content and distribution as well as the corresponding acidity in SSZ-13 zeolite determine the catalytic performance of the zeolite for different catalytic reactions. Herein, quantum chemical computing using density functional theory (DFT) combined with multinuclear solid-state nuclear- magnetic-resonance (NMR) experiments were performed to investigate the correlation of Al location and Brønsted acidity of H-SSZ-13 zeolite with the Si/Al ratio varying from 5.8 to 25. The most favorable acid site in the 1Al model is O(1)―H in which a proton is bonded with the O(1) atom near the isolated Al atom of the zeolite framework. Nevertheless, energy differences were rather small when comparing the substitution energies of an Al atom replacing a Si atom in the zeolite framework with a proton located in different O sites. As the Si/Al ratio decreased, the Al-rich SSZ-13 zeolite contained more Al substitutions in its framework. This system exhibited the lowest substitution energy when two Al atoms were located at the diagonal of the same six-membered ring for the Al-Si-Si-Al (NNNN) sequence in the framework of the Al-rich SSZ-13 zeolite. However, for the Al-Si-Al (NNN) sequence, the most favorable distribution involved two Al atoms located in different six-membered rings of the double six-membered ring units (D6R). The proton affinities (PA), NH₃ desorption energies, and ¹H NMR chemical shifts after d3-acetonitrile adsorption were calculated in the most stable models to characterize the Brønsted acid strength of the SSZ-13 zeolite with different Si/Al ratios. All computing results suggested that the Al-rich SSZ-13 zeolite exhibited weaker Brønsted acid strength than that of the Si-rich counterpart due to the presence of Si(2Al) groupings with the NNN sequence in the framework. Quantitative ²⁹Si magic-angle spinning (MAS) NMR measurements after deconvolution demonstrated that the content of Si(2Al) groupings in the Al-rich SSZ-13 was > 43%. The ¹H MAS NMR experiments after d3-acetonitrile adsorption showed that the chemical shift of the bridging hydroxyls in the Al-rich SSZ-13 moved to the lower field, further confirming that it had a weaker Brønsted acid strength than the Si-rich counterpart.
- DFT,
- Solid-state NMR,
- SSZ-13 zeolite,
- Al distribution,
- Brønsted acidity
1. [1]
  Yang, B.; Guo, C.; Cheng, J. Chem. Eng. Prog. 2014, 33, 368. doi: 10.3969/j.issn.1000-6613.2014.02.018
2. [2]
  Zhang, R.; Liu, N.; Lei, Z.; Chen, B. Chem. Rev. 2016, 116, 3658. doi: 10.1021/acs.chemrev.5b00474 doi: 10.1021/acs.chemrev.5b00474
3. [3]
  Zhou, Z.; Wang, Z.; Liu, Z. Sci. China Chem. 2018, 48, 562. doi: 10.1360/N032017-00215
4. [4]
  Bull, I.; Boorse, R. S.; Jaglowski, W. M.; Koermer, G. S.; Moini, A.; Patchett, J. A.; Xue, W.; Burk, P.; Dettling, J. C.; Caudle, M. T. Processes for Reducing Nitrogen Oxides Using Copper Cha Zeolite Catalysts. U.S. Patent 8404203.B2, 3013-03-26
5. [5]
  Beale, A. M.; Gao, F.; Lezcano-Gonzalez, I.; Peden, C. H. F.; Szanyi, J. Chem. Soc. Rev. 2015, 44, 7371. doi: 10.1039/c5cs00108k doi: 10.1039/c5cs00108k
6. [6]
  Song, J.; Wang, Y.; Walter, E. D.; Washton, N. M.; Mei, D.; Kovarik, L.; Engelhard, M. H.; Prodinger, S.; Wang, Y.; Peden, C. H. F.; et al. ACS Catal. 2017, 7, 8214. doi: 10.1021/acscatal.7b03020 doi: 10.1021/acscatal.7b03020
7. [7]
  Yu, H.; Zhang, G.; Han, L.; Chang, L.; Bao, W.; Wang, J. Acta Phys. -Chim. Sin. 2015, 31, 2165. doi: 10.3866/PKU.WHXB201509184
8. [8]
  Zhao, Z.; Yu, R.; Zhao, R.; Shi, C.; Gies, H.; Xiao, F.; De Vos, D.; Yokoi, T.; Bao, X.; Kolb, U.; et al. Appl. Catal. B: Environ. 2017, 217, 421. doi: 10.1016/j.apcatb.2017.06.013 doi: 10.1016/j.apcatb.2017.06.013
9. [9]
  Gao, F.; Wang, Y.; Washton, N. M.; Kollar, M.; Szanyi, J.; Peden, C. H. F. J. Catal. 2015, 331, 25. doi: 10.1016/j.jcat.2015.08.004 doi: 10.1016/j.jcat.2015.08.004
10. [10]
  Deimund, M. A.; Harrison, L.; Lunn, J. D.; Liu, Y.; Malek, A.; Shayib, R.; Davis, M. E. ACS Catal. 2016, 6, 542. doi: 10.1021/acscatal.5b01450 doi: 10.1021/acscatal.5b01450
11. [11]
  Di Iorio, J. R.; Nimlos, C. T.; Gounder, R. ACS Catal. 2017, 7, 6663. doi: 10.1021/acscatal.7b01273 doi: 10.1021/acscatal.7b01273
12. [12]
  Zhao, Z.; Xing, Y.; Li, S.; Meng, X.; Xiao, F.; McGuire, R.; Parvulescu, A. N.; Müller, U.; Zhang, W. J. Phys. Chem. C 2018, 122, 9973. doi: 10.1021/acs.jpcc.8b01423 doi: 10.1021/acs.jpcc.8b01423
13. [13]
  Civalleri, B.; Ferrari, A. M.; Llunell, M.; Orlando, R.; Mérawa, M.; Ugliengo, P. Chem. Mater. 2003, 15, 3996. doi: 10.1021/cm0342804 doi: 10.1021/cm0342804
14. [14]
  Zheng, A.; Chen, L.; Yang, J.; Zhang, M.; Su, Y.; Yue, Y.; Ye, C.; Deng, F. J. Phys. Chem. B 2005, 109, 24273. doi: 10.1021/jp0527249 doi: 10.1021/jp0527249
15. [15]
  Zheng, A.; Liu, S. B.; Deng, F. Chem. Rev. 2017, 117, 12475. doi: 10.1021/acs.chemrev.7b00289 doi: 10.1021/acs.chemrev.7b00289
16. [16]
  Li, S.; Li, J.; Zheng, A.; Deng, F. Acta Phys. -Chim. Sin. 2017, 33, 270. doi: 10.3866/PKU.WHXB201611022
17. [17]
  Sazama, P.; Tabor, E.; Klein, P.; Wichterlova, B.; Sklenak, S.; Mokrzycki, L.; Pashkkova, V.; Ogura, M.; Dedecek, J. J. Catal. 2016, 333, 102. doi: 10.1016/j.jcat.2015.10.010 doi: 10.1016/j.jcat.2015.10.010
18. [18]
  Zhang, W.; Xu, S.; Han, X.; Bao, X. Chem. Soc. Rev. 2012, 41 (1), 192. doi: 10.1039/c1cs15009j doi: 10.1039/c1cs15009j
19. [19]
  Shah, R.; Gale, J. D.; Payne, M. C. J. Phys. Chem-Us 1996, 100, 11688. doi: 10.1021/Jp960365z doi: 10.1021/Jp960365z
20. [20]
  Lo, C.; Trout, B. L. J. Catal. 2004, 227 (1), 77. doi: 10.1016/j.jcat.2004.06.018 doi: 10.1016/j.jcat.2004.06.018
21. [21]
  Solans-Monfort, X.; Sodupe, M.; Branchadell, V.; Sauer, J.; Orlando, R.; Ugliengo, P. J. Phys. Chem. B 2005, 109, 3539. doi: 10.1021/jp045531e doi: 10.1021/jp045531e
22. [22]
  Haw, J. F.; Hall, M. B.; Alvarado-Swaisgood, A. E.; Munson, E. J.; Lin, Z.; Beck, L. W.; Howard, T. J. Am. Chem. Soc. 1994, 116, 7308. doi: 10.1021/ja00095a039 doi: 10.1021/ja00095a039
23. [23]
  Gil, B.; Zones, S. I.; Hwang, S. J.; Bejblová, M.; Čejka, J. J. Phys. Chem. C 2008, 112, 2997. doi: 10.1021/jp077687v doi: 10.1021/jp077687v
24. [24]
  Calligaris, M.; Nardin, G.; Randaccio, L. Zeolites 1983, 3, 205. doi: 10.1016/0144-2449(83)90008-8 doi: 10.1016/0144-2449(83)90008-8
25. [25]
  Zheng, A.; Zhang, H.; Chen, L.; Yue, Y.; Ye, C.; Deng, F. J. Phys. Chem. B 2007, 111, 3085. doi: 10.1021/jp067340c doi: 10.1021/jp067340c
26. [26]
  Dunning, T. H. J. Phys. Chem. A 2000, 104, 9062. doi: 10.1021/jp001507z doi: 10.1021/jp001507z
27. [27]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; et al. Gaussian 09, Revision D.01; Gaussian Inc: Wallingford, CT, 2013
28. [28]
  Jobic, H.; Tuel, A.; Krossner, M.; Sauer, J. J. Phys. Chem. C 1996, 100, 19545. doi: 10.1021/jp9619954 doi: 10.1021/jp9619954
29. [29]
  Zygmunt, S. A.; Curtiss, L. A.; Iton, L. E.; Erhardt, M. K. J. Phys. Chem-Us 1996, 100, 6663. doi: 10.1021/Jp952913z doi: 10.1021/Jp952913z
30. [30]
  Ryder, J. A.; Chakraborty, A. K.; Bell, A. T. J. Phys. Chem. B 2000, 104, 6998. doi: 10.1021/jp9943427 doi: 10.1021/jp9943427
31. [31]
  Wang, J.; Li, S.; Zhao, Z.; Zhou, D.; Lu, A.; Zhang, W. Acta Phys. -Chim. Sin. 2016, 32, 1666. doi: 10.3866/PKU.WHXB201604012
32. [32]
  Li, S.; Zhao, Z.; Zhao, R.; Zhou, D.; Zhang, W. ChemCatChem 2017, 9, 1494. doi: 10.1002/cctc.201601623 doi: 10.1002/cctc.201601623
33. [33]
  Zhao, R.; Zhao, Z.; Li, S.; Zhang, W. J. Phys. Chem. Lett. 2017, 8, 2323. doi: 10.1021/acs.jpclett.7b00711 doi: 10.1021/acs.jpclett.7b00711
34. [34]
  Calligaris, M.; Nardin, G.; Randaccio, L.; Chiaramonti, P. C. Acta Crystallogr. B 1982, 38, 602. doi: Doi10.1107/S0567740882003483 doi: 10.1107/S0567740882003483
35. [35]
  Jeanvoine, Y.; Angyan, J. G.; Kresse, G.; Hafner, J. J. Phys. Chem. B 1998, 102, 5573. doi: 10.1021/Jp980341n doi: 10.1021/Jp980341n
36. [36]
  Nielsen, M.; Brogaard, R. Y.; Falsig, H.; Beato, P.; Swang, O.; Svelle, S. ACS Catal. 2015, 5, 7131. doi: 10.1021/acscatal.5b01496 doi: 10.1021/acscatal.5b01496
37. [37]
  Smith, L. J.; Davidson, A.; Cheetham, A. K. Catal. Lett. 1997, 49, 143. doi: 10.1023/A:1019097019846 doi: 10.1023/A:1019097019846
38. [38]
  Wang, N.; Zhang, M.; Yu, Y. Micropor. Mesopor. Mat. 2013, 169, 47. doi: 10.1016/j.micromeso.2012.10.019 doi: 10.1016/j.micromeso.2012.10.019
39. [39]
  Chai, J. D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615. doi: 10.1039/b810189b doi: 10.1039/b810189b
40. [40]
  Jänchen, J.; Van Wolput, J. H. M. C.; Van de Ven, L. J. M.; De Haan, J. W.; Van Santen, R. A. Catal. Lett. 1996, 39, 147. doi: 10.1007/bf00805574 doi: 10.1007/bf00805574
41. [41]
  Dai, W.; Sun, X.; Tang, B.; Wu, G.; Li, L.; Guan, N.; Hunger, M. J. Catal. 2014, 314, 10. doi: 10.1016/j.jcat.2014.03.006 doi: 10.1016/j.jcat.2014.03.006
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