五配位铝强化硅铝固体酸的固体核磁共振研究

doi:10.11938/cjmr20212930

摘要/Abstract

摘要：

Brønsted酸（B酸）是无定型硅铝（ASAs）表面最重要的催化活性位点.通常认为B酸位的形成只依赖于不饱和四配位铝（Al^IV），且仅具有弱B酸性.通过合成五配位铝（Al^V）富集的ASAs能够大幅提升高铝硅比（Al/Si）时的B酸含量及强度，克服传统Al^IV富集的ASAs的酸性强化瓶颈.本文介绍了Al^V在ASAs酸性强化及合成单原子催化剂中的重要作用.通过采用多种二维固体核磁共振（SSNMR）及原位质子NMR技术，证明了Al^V能够大量富集在ASAs表面，着重介绍了两种基于Al^V的新B酸位的形成机制，并阐明了Al^V诱导单原子催化剂在ASAs表面形成的机理.

关键词: 固体核磁共振（SSNMR）, 无定型硅铝固体酸催化剂, 五配位铝, 结构-酸性关系, 固体酸催化

Abstract:

Brønsted acid sites (BASs) on amorphous silica-aluminas (ASAs) are key active sites that can be generated based on tetra-coordinated aluminum (Al^IV) species, albeit much weaker than that of zeolites. Penta-coordinated aluminum (Al^V) species are recently reported to enhance the acidity of ASAs, and to overcome the limitations of Al^IV species. This review introduces novel strategies to control the synthesis of Al^V-enriched ASAs using flame spray pyrolysis (FSP) techniques. The acidic properties and local structure of Al^V-enriched ASAs were characterized by various advanced 2D solid-state nuclear magnetic resonance (SSNMR) techniques and in situ ¹H MAS NMR experiments, showing two new types of BASs from moderate to zeolitic acid strength based on Al^V species. ²⁷Al and ¹H MAS NMR studies uncovered the role of Al^V species in tailoring single-atom catalysts on ASAs.

Key words: solid-state nuclear magnetic resonance (SSNMR), amorphous silica-aluminas, penta-coordinated aluminum, structure-acidity relationship, solid acid catalysis

中图分类号:

O482.53

王子春,黄骏,姜怡娇. 五配位铝强化硅铝固体酸的固体核磁共振研究[J]. 波谱学杂志, 2021, 38(4): 552-570.

Zi-chun WANG,Jun HUANG,Yi-jiao JIANG. Solid-State NMR Spectroscopy Studies of Enhanced Acidity of Silica-Aluminas Based on Penta-Coordinated Aluminum Species[J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 552-570.

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Position	Catalysts	Al^IV (at. %)^a	Al^V (at. %)^a	Al^VI (at. %)^a	BAS density (mmol/g)^b
1	SA/10	62	37	1	9.8×10^-2
2	SA/30	51	48	1	11.1×10^-2
3	SA/50	42	51	7	13.4×10^-2
4	SA/70	41	55	4	15.1×10^-2

Position	Catalyst	ABET/(m²/g) ^a	YEM/% ^b	SEM/% ^b	BAS/(mmol/g) ^c	LAS/(mmol/g) ^c	TOFs/h-1 ^b
1	SA/0	156	0	0	0	0	0
2	SA/10	377	56	93	0.098	0	10.2
3	SA/30	248	67	94	0.111	0	10.5
4	SA/50	222	81	95	0.134	0.003	10.5
5	SA/70	200	97	97	0.151	0.008	10.5
6	De-Al-HY	671	81	90	0.865	1.75	0.57

	Temp/K	Time/h	Conversion/%	Yield/%	Ref.
Fe-ZSM-5, Si/Al=22.8	468	2.5	90	33	[60]
ASA, Si/Al=90/10 ^a	433	2	45	18.8	[8]
SA/10, Si/Al=90/10	433	2	23	6.3	[8]
SA/50, Si/Al=50/50	433	2	70 (68) ^b	38 (37) ^b	[8]

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