An advanced approach for measuring acidity of hydroxyls in confined space: a FTIR study of low-temperature CO and (15)N2 adsorption on MOF samples from the MIL-53(Al) series

Physical Chemistry Chemical Physics : PCCP
M MihaylovKonstantin Hadjiivanov

Abstract

Acidity of solids is decisive for their interaction with guest molecules. One of the most used methods for measuring the acidity of surface hydroxyl groups is the hydrogen bond method based on the spectral shift of the OH stretching modes induced by the adsorption of weak bases. However, many materials of practical interest (e.g. metal organic frameworks, zeolites, etc.) are porous and the OH groups are involved in H-bonding with framework basic sites. Here we show that MIL-53(Al) and NH2-MIL-53(Al) samples are characterized by one type of structural hydroxyl but three IR bands are detected at 100 K with these materials (at 3721, 3711 and 3683 cm(-1)). These bands are assigned to structural hydroxyls involved in H-bonding with different strengths. There is no correlation between the acidities of the hydroxyls, as measured by low-temperature CO or (15)N2 adsorption, and the main reason for this is the pre-existing H-bond. A method for the estimation of the intrinsic frequency of the OH groups (i.e. if not participating in H-bonds), based on the analysis of the spectral data obtained with two molecular probes, is proposed. According to this method, the OH stretching frequency of the structural hydroxyls of MIL-53(Al) samples is d...Continue Reading

References

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Feb 20, 2014·Physical Chemistry Chemical Physics : PCCP·Carlos O AreanPavla Chlubná-Eliášová

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Citations

Dec 15, 2015·Chemical Communications : Chem Comm·M MihaylovK Hadjiivanov
Mar 25, 2017·Chemical Society Reviews·S M J RoggeJ Gascon
Feb 17, 2018·The Journal of Physical Chemistry. C, Nanomaterials and Interfaces·Alexander E J HoffmanVeronique Van Speybroeck
Nov 11, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Muhammad UsmanAasif Helal

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