H-MCM-22 沸石分子筛中 Brønsted/Lewis 酸协同效应的 1H 和 27Al 双量子魔角旋转固体核磁共振研究

doi:10.1016/S1872-2067(10)60287-2

催化学报 ›› 2012, Vol. 33 ›› Issue (1): 129-139.DOI: 10.1016/S1872-2067(10)60287-2

H-MCM-22 沸石分子筛中 Brønsted/Lewis 酸协同效应的 ¹H 和 ²⁷Al 双量子魔角旋转固体核磁共振研究

喻志武 1,2, 王强 1, 陈雷 1, 邓风 1,*

1中国科学院武汉物理与数学研究所, 波谱与原子分子物理国家重点实验室, 武汉磁共振中心, 湖北武汉 430071; 2中国科学院强磁场科学中心, 安徽合肥 230031

收稿日期:2011-07-28 修回日期:2011-09-02 出版日期:2012-01-16 发布日期:2015-05-26

Brønsted/Lewis Acid Sites Synergy in H-MCM-22 Zeolite Studied by ¹H and ²⁷Al DQ-MAS NMR Spectroscopy

YU Zhiwu1,2, WANG Qiang1, CHEN Lei1, DENG Feng1,*

1Wuhan Center for Magnetic Resonance, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, Hubei, China; 2High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei 230031, Anhui, China

Received:2011-07-28 Revised:2011-09-02 Online:2012-01-16 Published:2015-05-26

摘要/Abstract

摘要： 采用各种固体核磁共振 (NMR) 技术详细研究了 H-MCM-22 分子筛中 Brønsted/Lewis 酸的协同效应. 二维 1H 双量子魔角旋转 (DQ-MAS) NMR 结果表明, 在脱铝 H-MCM-22 分子筛中 Brønsted 酸位 (骨架桥式羟基) 和 Lewis 酸位 (非骨架铝羟基) 之间是空间邻近的, 暗示着可能存在 B/L 酸协同效应. 二维 27Al DQ-MAS NMR 结果揭示了各种铝物种之间的空间邻近性, 表明 B/L 酸协同效应优先发生在 H-MCM-22 分子筛超笼中的骨架 T6 位铝和非骨架铝物种之间. 2-13C-丙酮探针分子实验发现, 因 B/L 酸协同效应而导致脱铝 H-MCM-22 分子筛酸性明显增强, 氘代吡啶探针分子实验也证实在 H-MCM-22 分子筛的超笼中发生了 B/L 酸协同效应. 上述结果将有助于我们理解在脱铝 H-MCM-22 分子筛上发生的多相催化机理.

关键词: H-MCM-22 分子筛, 脱铝, 酸性, Brønsted/Lewis 酸协同效应, 双量子魔角旋转核磁共振

Abstract: Brønsted/Lewis acid sites synergy in H-MCM-22 zeolite was studied by solid-state nuclear magnetic resonance (NMR). Two-dimensional ¹H double quantum-magic angle spinning (DQ-MAS) NMR revealed the details of the spatial relationship between the Lewis and the Brønsted acid sites in a dealuminated H-MCM-22 zeolite, which implied the existence of a Brønsted/Lewis acid sites synergy. Two-dimensional ²⁷Al DQ-MAS NMR was used to give the details of the spatial proximities of various aluminum species. The Brønsted/Lewis acid sites synergy occurred in the supercage of the H-MCM-22 zeolite between a T₆ site Al and extra-framework Al species. ¹³C CP/MAS NMR of adsorbed acetone demonstrated that the spatial proximities of the Brønsted and Lewis acid sites led to a synergy that enhanced the Brønsted acid strength of the dealuminated zeolites. ¹H MAS NMR of adsorbed deuterated pyridine confirmed that the Brønsted/Lewis acid sites synergy occurred in the supercage of H-MCM-22. This finding is important for understanding the mechanism of acid-catalyzed reactions on H-MCM-22 zeolites.

Key words: H-MCM-22 zeolite, dealumination, acidity, Brønsted/Lewis acid synergy, double quantum-magic angle spinning nuclear magnetic resonance

喻志武, 王强, 陈雷, 邓风. H-MCM-22 沸石分子筛中 Brønsted/Lewis 酸协同效应的 ¹H 和 ²⁷Al 双量子魔角旋转固体核磁共振研究[J]. 催化学报, 2012, 33(1): 129-139.

YU Zhi-Wu, WANG Qiang, CHEN Lei, DENG Feng. Brønsted/Lewis Acid Sites Synergy in H-MCM-22 Zeolite Studied by ¹H and ²⁷Al DQ-MAS NMR Spectroscopy[J]. Chinese Journal of Catalysis, 2012, 33(1): 129-139.

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H-MCM-22 沸石分子筛中 Brønsted/Lewis 酸协同效应的 ¹H 和 ²⁷Al 双量子魔角旋转固体核磁共振研究

Brønsted/Lewis Acid Sites Synergy in H-MCM-22 Zeolite Studied by ¹H and ²⁷Al DQ-MAS NMR Spectroscopy

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