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作为沸石酸度探针的核自旋弛豫:HZSM-5中吡啶的核磁共振与程序升温脱附联合研究

Nuclear spin relaxation as a probe of zeolite acidity: a combined NMR and TPD investigation of pyridine in HZSM-5.

作者信息

Robinson Neil, Bräuer Pierre, York Andrew P E, D'Agostino Carmine

机构信息

Department of Chemical Engineering, University of Western Australia, 35 Stirling Highway, Perth, WA 6009, Australia.

出版信息

Phys Chem Chem Phys. 2021 Sep 7;23(33):17752-17760. doi: 10.1039/d1cp01515j. Epub 2021 Jun 30.

Abstract

The relative surface affinities of pyridine within microporous HZSM-5 zeolites are explored using two-dimensional H nuclear magnetic resonance (NMR) relaxation time measurements. The dimensionless ratio of longitudinal-to-transverse nuclear spin relaxation times T/T is shown to exhibit strong sensitivity to the silica/alumina ratio (SAR) of these zeolites, which is indicative of material acidity. This trend is interpreted in terms of increased pyridine surface affinity with decreasing SAR. Temperature programmed desorption (TPD) analysis corroborates this observation, revealing a distinct increase in the heat of desorption associated with adsorbed pyridine as a function of decreasing SAR. A direct correlation between NMR and TPD data suggests NMR relaxation time analysis can be a valuable tool for the non-invasive characterisation of adsorption phenomena in microporous solids.

摘要

利用二维氢核磁共振(NMR)弛豫时间测量技术,探究了吡啶在微孔HZSM - 5沸石中的相对表面亲和力。纵向与横向核自旋弛豫时间的无量纲比值T/T对这些沸石的硅铝比(SAR)表现出强烈的敏感性,这表明了材料的酸度。这种趋势可解释为随着SAR的降低,吡啶表面亲和力增加。程序升温脱附(TPD)分析证实了这一观察结果,揭示了与吸附吡啶相关的脱附热随SAR降低而明显增加。NMR和TPD数据之间的直接相关性表明,NMR弛豫时间分析可以成为一种用于微孔固体吸附现象非侵入性表征的有价值工具。

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