固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布

doi:10.11938/cjmr20212906

摘要/Abstract

摘要：

具有AEI结构的SSZ-39分子筛的骨架外阳离子落位和铝分布对其催化性能影响显著.AEI笼中有三个结晶学不等价位，且铝取代T位具有一定的倾向性.本文结合固体核磁共振（NMR）技术（²⁷Al/²³Na MQ MAS NMR），以及密度泛函理论（DFT）计算，研究了不同硅铝比Na-SSZ-39分子筛中的Na⁺落位和铝分布.在孤立铝分布的情况下，铝原子优先占据于T3位，Na⁺主要落位于AEI笼中的SIIa0和SIII'a0位点上，其中SIII'a0位点的优先度较高，此外少部分Na⁺还落位于六棱柱内部的SIa0.当铝对存在时，AlSiSiAl分布的铝对占据六元环的对位（T3-T3），对应的Na⁺分别落位于SIIa1和SⅢ'a1位点.随着分子筛结构的部分破坏，游离的Na⁺可能形成明显的SIII'b位点.本文可加深对SSZ-39分子筛构效关系的理解，为更好地调控催化性能奠定基础.

关键词: 固体核磁共振, SSZ-39分子筛, 铝分布, 阳离子落位, 密度泛函理论（DFT）计算

Abstract:

The catalytic performance of zeolite SSZ-39 with AEI structure is significantly affected by the locations of its extra-framework cation and aluminum distributions. The AEI cage contains three crystallographically inequivalent T sites that tend to be substituted by aluminum. In this work, the Na⁺ locations and Al distributions in Na-SSZ-39 with different Si/Al ratios were studied by ²⁷Al/²³Na MQ MAS NMR spectroscopy together with density functional theory (DFT) calculations. For isolated Al substitution, the T3 site was found to be preferentially occupied by Al, and Na⁺ was mainly located in the 6-MR (SIIa0) or 8-MR (SIII'a0) sites of the AEI cage, although the priority of SIII'a0 site was slightly higher, and minor Na⁺ was located inside the hexagonal prism (SIa0). For paired Al substitution, stable AlSiSiAl structure was found to be located in 6-MR, and the corresponding Na⁺ cations were located at SIIa1 and SIII'a1 sites, respectively. In post-modified zeolites with partial destruction of the framework structure, some free Na⁺ cations were found to form distinct SIII'b sites. This study deepened the understanding on the structure-reactivity correlation of SSZ-39 zeolite and provided insights into how to fine-tune its catalytic performance.

Key words: solid-state nuclear magnetic resonance, SSZ-39 zeolite, Al distribution, cation location, density functional theory (DFT) calculations

中图分类号:

O482.53

陈翰迪,孔海宇,赵侦超,张维萍. 固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布[J]. 波谱学杂志, 2021, 38(4): 543-551.

Han-di CHEN,Hai-yu KONG,Zhen-chao ZHAO,Wei-ping ZHANG. Exploring the Na⁺ Locations and Al Distributions in SSZ-39 Zeolite by Solid-State NMR Spectroscopy and DFT Calculations[J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 543-551.

图/表 8

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		Al_IV-1	Content/%	Al_IV-2	Content/%	Al_VI	Content/%
Na-SSZ-39(20)	δ_iso/ppm	63		58		1
	C_q/MHz	3.5	65	4.8	22	3.5	13
	η	0.6±0.1		0.3±0.1		0.5±0.1
Na-SSZ-39(14)	δ_iso/ppm	63		58		0
	C_q/MHz	3.6	39	5.8	55	1.9	6
	η	0.6±0.1		0.2±0.1		0.3±0.1
Na-SSZ-39(6)	δ_iso/ppm	63		59
	C_q/MHz	3.6	62	4.6	38	/	/
	η	0.6±0.1		0.2±0.1

		SIa0	SIIa0	SIIa1	SIII’a0	SIII’a1	SIII’b
Na-SSZ-39(20)	δ_iso/ppm	5±1.0		-10±1.0	-31±2.0	-38±1.0	-10±1.0
	C_q/MHz	1.9±0.1	/	3.8±0.2	2.4±0.1	2.7±0.2	2.7±0.1
	η	0.6±0.1		0.3±0.1	0.6±0.1	0.3±0.1	0.5±0.1
Na-SSZ-39(14)	δ_iso/ppm	4±1.0	-20±2.0	-9±2.0	-31±2.0	-38±2.0
	C_q/MHz	1.8±0.1	3.0±0.2	4.0±0.2	2.5±0.1	2.7±0.2	/
	η	0.6±0.1	0.7±0.1	0.3±0.1	0.6±0.1	0.3±0.1
Na-SSZ-39(6)	δ_iso/ppm	5±1.0	-20±2.0		-32±2.0	-38±1.0	-9±2.0
	C_q/MHz	2.6±0.1	3.0±0.2	/	2.5±0.1	2.7±0.2	2.7±0.1
	η	0.6±0.1	0.7±0.1		0.6±0.1	0.3±0.1	0.4±0.1
Calculated results	δ_iso/ppm		-22	-11	-34	-38
	C_q/MHz	/	3.4	4.2	2.8	2.5	/
	η		0.5	0.7	0.5	0.5

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