DFT计算结合固体NMR研究富铝SSZ-13的铝分布和Brønsted酸性

doi:10.3866/PKU.WHXB201903021

Abstract

Abstract:

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.

Key words: DFT, Solid-state NMR, SSZ-13 zeolite, Al distribution, Brønsted acidity

Shihan Li,Zhenchao Zhao,Shikun Li,Youdong Xing,Weiping Zhang. 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), 1903021. doi: 10.3866/PKU.WHXB201903021

Figures/Tables 10

Fig 1

Fig 2

Table 1

Fig 3

Table 2

Table 3

Fig 4

Fig 5

Table 4

Fig 6

References 41

1	Yang B. ; Guo C. ; Cheng J. Chem. Eng. Prog. 2014, 33, 368. doi: 10.3969/j.issn.1000-6613.2014.02.018
	杨博; 郭翠梨; 程景耀. 化工进展, 2014, 33, 368. doi: 10.3969/j.issn.1000-6613.2014.02.018
2	Zhang R. ; Liu N. ; Lei Z. ; Chen B. Chem. Rev. 2016, 116, 3658. doi: 10.1021/acs.chemrev.5b00474
3	Zhou Z. ; Wang Z. ; Liu Z. Sci. China Chem. 2018, 48, 562. doi: 10.1360/N032017-00215
	周子正; 王智华; 刘志明. 中国科学:化学, 2018, 48, 562. doi: 10.1360/N032017-00215
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	Beale A. M. ; Gao F. ; Lezcano-Gonzalez I. ; Peden C. H. F. ; Szanyi J. Chem. Soc. Rev. 2015, 44, 7371. doi: 10.1039/c5cs00108k
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
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
	俞华峰; 张国佩; 韩丽娜; 常丽萍; 鲍卫仁; 王建成. 物理化学学报, 2015, 31, 2165. doi: 10.3866/PKU.WHXB201509184
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
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
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
11	Di Iorio J. R. ; Nimlos C. T. ; Gounder R. ACS Catal. 2017, 7, 6663. doi: 10.1021/acscatal.7b01273
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
13	Civalleri B. ; Ferrari A. M. ; Llunell M. ; Orlando R. ; Mérawa M. ; Ugliengo P. Chem. Mater. 2003, 15, 3996. doi: 10.1021/cm0342804
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
15	Zheng A. ; Liu S. B. ; Deng F. Chem. Rev. 2017, 117, 12475. doi: 10.1021/acs.chemrev.7b00289
16	Li S. ; Li J. ; Zheng A. ; Deng F. Acta Phys. -Chim. Sin. 2017, 33, 270. doi: 10.3866/PKU.WHXB201611022
	李申慧; 李静; 郑安民; 邓风. 物理化学学报, 2017, 33, 270. doi: 10.3866/PKU.WHXB201611022
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
18	Zhang W. ; Xu S. ; Han X. ; Bao X. Chem. Soc. Rev. 2012, 41 (1), 192. doi: 10.1039/c1cs15009j
19	Shah R. ; Gale J. D. ; Payne M. C. J. Phys. Chem-Us 1996, 100, 11688. doi: 10.1021/Jp960365z
20	Lo C. ; Trout B. L. J. Catal. 2004, 227 (1), 77. doi: 10.1016/j.jcat.2004.06.018
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
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
23	Gil B. ; Zones S. I. ; Hwang S. J. ; Bejblová M. ; Čejka J. J. Phys. Chem. C 2008, 112, 2997. doi: 10.1021/jp077687v
24	Calligaris M. ; Nardin G. ; Randaccio L. Zeolites 1983, 3, 205. doi: 10.1016/0144-2449(83)90008-8
25	Zheng A. ; Zhang H. ; Chen L. ; Yue Y. ; Ye C. ; Deng F. J. Phys. Chem. B 2007, 111, 3085. doi: 10.1021/jp067340c
26	Dunning T. H. J. Phys. Chem. A 2000, 104, 9062. doi: 10.1021/jp001507z
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	Jobic H. ; Tuel A. ; Krossner M. ; Sauer J. J. Phys. Chem. C 1996, 100, 19545. doi: 10.1021/jp9619954
29	Zygmunt S. A. ; Curtiss L. A. ; Iton L. E. ; Erhardt M. K. J. Phys. Chem-Us 1996, 100, 6663. doi: 10.1021/Jp952913z
30	Ryder J. A. ; Chakraborty A. K. ; Bell A. T. J. Phys. Chem. B 2000, 104, 6998. doi: 10.1021/jp9943427
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
	王娟; 李世坤; 赵侦超; 周丹红; 陆安慧; 张维萍. 物理化学学报, 2016, 32, 1666. doi: 10.3866/PKU.WHXB201604012
32	Li S. ; Zhao Z. ; Zhao R. ; Zhou D. ; Zhang W. ChemCatChem 2017, 9, 1494. doi: 10.1002/cctc.201601623
33	Zhao R. ; Zhao Z. ; Li S. ; Zhang W. J. Phys. Chem. Lett. 2017, 8, 2323. doi: 10.1021/acs.jpclett.7b00711
34	Calligaris M. ; Nardin G. ; Randaccio L. ; Chiaramonti P. C. Acta Crystallogr. B 1982, 38, 602. doi: 10.1107/S0567740882003483
35	Jeanvoine Y. ; Angyan J. G. ; Kresse G. ; Hafner J. J. Phys. Chem. B 1998, 102, 5573. doi: 10.1021/Jp980341n
36	Nielsen M. ; Brogaard R. Y. ; Falsig H. ; Beato P. ; Swang O. ; Svelle S. ACS Catal. 2015, 5, 7131. doi: 10.1021/acscatal.5b01496
37	Smith L. J. ; Davidson A. ; Cheetham A. K. Catal. Lett. 1997, 49, 143. doi: 10.1023/A:1019097019846
38	Wang N. ; Zhang M. ; Yu Y. Micropor. Mesopor. Mat. 2013, 169, 47. doi: 10.1016/j.micromeso.2012.10.019
39	Chai J. D. ; Head-Gordon M. Phys. Chem. Chem. Phys. 2008, 10, 6615. doi: 10.1039/b810189b
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
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

O sites	E_rel(2AlH/Si)/(kJ•mol⁻¹)
O sites	M1^a	M2 ^b
O1	0	0
O2	5.9	8.4
O3	2.9	4.6
O4	6.3	6.3

Al-Si-Si-Al	E_rel(2AlH/Si)/(kJ•mol⁻¹)		Al-Si-Al	E_rel(2AlH/Si)/(kJ•mol⁻¹)
Al-Si-Si-Al	M1 ^a	M2 ^b	Al-Si-Al	M1	M2
NNNN-1-O1O1-H	0	0	NNN-1-O1O1-H	45.6	43.1
NNNN-1-O3O1-H	0.8	5.4	NNN-1-O1O3-H	41.0	42.3
NNNN-1-O3O3-H	26.8	32.7	NNN-1-O3O3-H	24.7	25.1
NNNN-2-O1O1-H	4.6	5.4	NNN-2-O1O1-H	0	0
NNNN-2-O1O3-H	10.9	17.2	NNN-2-O1O3-H	77.0	77.9
NNNN-2-O3O3-H	26.4	33.9	NNN-2-O3O3-H	38.1	40.6

Types	E_PA/(kJ•mol⁻¹)		d_(NH₃-H) ^c/Å	d_(NH₄⁺-O) ^d/Å	E_des/(kJ•mol⁻¹)
Types	M1 ^a	M2 ^b	d_(NH₃-H) ^c/Å	d_(NH₄⁺-O) ^d/Å	E_des/(kJ•mol⁻¹)
1Al-O1	1179.0	1192.4	1.06	1.62/2.01/2.61	133.6
NNNN-1-O1O1-H	1269.4	1286.2	1.07	1.59/2.05/2.69	130.6
NNN-2-O1O1-H	1823.4	1854.8	1.10	1.49/2.27/2.48	124.3

Types	d_(N―H)/Å ^a	∠_NO1O1/(°)^b	Edes/(kJ•mol⁻¹)	¹H δ_cal ^c	¹H δ_ave ^d	¹H δ_exp ^e
1Al-CH3CN-1	1.62	30.8	99.2	10.8	10.9	11.0
1Al-CH3CN-2	1.63	25.5	103.0	10.9
NNNN-CH3CN-1	1.63/1.63	21.9/21.9	99.2	10.0/10.0	10.1	9.8
NNNN-CH3CN-2	1.63/1.62	21.7/28.0	101.3	10.0/10.1
NNNN-CH3CN-3	1.62/1.62	28.4/28.3	103.4	10.1/10.1
NNN-CH3CN-1	1.64/1.66	25.8/33.4	99.2	9.3/9.7	9.6
NNN-CH3CN-2	1.61/1.81	47.4/10.3	98.8	10.2/8.3
NNN-CH3CN-3	1.63/1.63	29.2/30.0	103.0	9.8/9.9

[1]	Lijun Zhang, Youlin Wu, Noritatsu Tsubaki, Zhiliang Jin. 2D/3D S-Scheme Heterojunction Interface of CeO₂-Cu₂O Promotes Ordered Charge Transfer for Efficient Photocatalytic Hydrogen Evolution [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2302051-.
[2]	Junhui Zhou, Zhimin Ao, Taicheng An. DFT Study of the Decomposition Mechanism of H₂S on V-Decorated Ti₂CO₂ Single-Atom Catalyst [J]. Acta Phys. -Chim. Sin., 2021, 37(8): 2007086-.
[3]	Zhen Wei, Minjie Li, Wencong Lu. Theoretical Study of High-Efficiency Organic Dyes with Different Electron-Withdrawing Groups Based on R6 toward Dye-Sensitized Solar Cells [J]. Acta Phys. -Chim. Sin., 2021, 37(10): 1905084-.
[4]	Fenfen Wang, Peng Wang, Hongyao Niu, Yingfeng Yu, Pingchuan Sun. Solid-State NMR Studies on Hydrogen Bonding Interactions and Structural Evolution in PAA/PEO Blends [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1912016-.
[5]	Chao Li, Ming Shen, Bingwen Hu. Solid-State NMR and EPR Methods for Metal Ion Battery Research [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1902019-.
[6]	Yi Ji, Lixin Liang, Changmiao Guo, Xinhe Bao, Tatyana Polenova, Guangjin Hou. Zero-Quantum Homonuclear Recoupling Symmetry Sequences in Solid-State Fast MAS NMR Spectroscopy [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1905029-.
[7]	Xiaolong Liu, Qiang Wang, Chao Wang, Jun Xu, Feng Deng. Hydrogen-Bond Induced Crystallization of Silicalite-1 Zeolite as Revealed by Solid-State NMR Spectroscopy [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1905035-.
[8]	Jing Deng,Tao Ma,Ziwei Chang,Weijing Zhao,Jun Yang. Determination of Three-Dimensional Structures of Protein Assemblies via Solid-State NMR [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1905019-.
[9]	Yuhong Li,Xin-Ping Wu,Cong Liu,Meng Wang,Benteng Song,Guiyun Yu,Gang Yang,Wenhua Hou,Xue-Qing Gong,Luming Peng. NMR and EPR Studies of Partially Reduced TiO₂ [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1905021-.
[10]	Yongchao Shi, Mingxue Tang. NMR/EPR Investigation of Rechargeable Batteries [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1905004-.
[11]	Zonghui Zhang, Jinjun Ren, Lili Hu. Structure Investigations on 100LiO_1/2-(100-x)PO_5/2-xTeO₂ Fast Ionic Conducting Glasses Using Solid-State Nuclear Magnetic Resonance Spectroscopy [J]. Acta Physico-Chimica Sinica, 2020, 36(11): 2001048-.
[12]	Paul GEERLINGS,Frank DE PROFT,Stijn FIAS. Analogies between Density Functional Theory Response Kernels and Derivatives of Thermodynamic State Functions [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 699-707.
[13]	Ulises OROZCO-VALENCIA,L. GÁZQUEZ José,Alberto VELA. Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 692-698.
[14]	Julia CONTRERAS-GARCíA,Weitao YANG. Perspective: Chemical Information Encoded in Electron Density [J]. Acta Phys. -Chim. Sin., 2018, 34(6): 567-580.
[15]	Jyotirmoy DEB,Debolina PAUL,David PEGU,Utpal SARKAR. Adsorption of Hydrazoic Acid on Pristine Graphyne Sheet: A Computational Study [J]. Acta Phys. -Chim. Sin., 2018, 34(5): 537-542.

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

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 41

Related Articles 15

Metrics

Recommended 0