Understanding adsorption processes at the molecular level, with multi-technique approaches, is nowadays at the frontier of porous materials research. In this work we show that with a proper data treatment, in situ high-resolution powder X-ray diffraction (HR-PXRD) at variable temperature and gas pressure can reveal atomic details of the accommodation sites, the framework dynamics as well as thermodynamic information (isosteric heat of adsorption) of the CO2 adsorption process in the robust iron(III) pyrazolate-based MOF Fe2 (BDP)3 [H2 BDP = 1,4-bis(1H-pyrazol-4-yl)benzene]. Highly reliable "HR-PXRD adsorption isotherms" can be constructed from CO2 molecules occupancy values. The "HR-PXRD adsorption isotherms" accurately match the results of conventional static and dynamic gas sorption experiments and Monte Carlo simulations. These results are indicative of the impact of the molecular-level behavior on the bulk properties of the system under study and of the potential of the presented multi-technique approach to understand adsorption processes in metal-organic frameworks.

CO2 Adsorption in a Robust Iron(III) Pyrazolate-Based MOF: Molecular-Level Details and Frameworks Dynamics From Powder X-Ray Diffraction Adsorption Isotherms / R. Vismara, S. Terruzzi, A. Maspero, T. Grell, F. Bossola, A. Sironi, S. Galli, J.A.R. Navarro, V. Colombo. - In: ADVANCED MATERIALS. - ISSN 0935-9648. - (2023). [Epub ahead of print] [10.1002/adma.202209907]

CO2 Adsorption in a Robust Iron(III) Pyrazolate-Based MOF: Molecular-Level Details and Frameworks Dynamics From Powder X-Ray Diffraction Adsorption Isotherms

S. Terruzzi
Secondo
;
T. Grell;A. Sironi;V. Colombo
Ultimo
2023

Abstract

Understanding adsorption processes at the molecular level, with multi-technique approaches, is nowadays at the frontier of porous materials research. In this work we show that with a proper data treatment, in situ high-resolution powder X-ray diffraction (HR-PXRD) at variable temperature and gas pressure can reveal atomic details of the accommodation sites, the framework dynamics as well as thermodynamic information (isosteric heat of adsorption) of the CO2 adsorption process in the robust iron(III) pyrazolate-based MOF Fe2 (BDP)3 [H2 BDP = 1,4-bis(1H-pyrazol-4-yl)benzene]. Highly reliable "HR-PXRD adsorption isotherms" can be constructed from CO2 molecules occupancy values. The "HR-PXRD adsorption isotherms" accurately match the results of conventional static and dynamic gas sorption experiments and Monte Carlo simulations. These results are indicative of the impact of the molecular-level behavior on the bulk properties of the system under study and of the potential of the presented multi-technique approach to understand adsorption processes in metal-organic frameworks.
CO2 adsorption; Metal-organic frameworks; Monte-Carlo simulations; cooperative adsorption; pyrazolates; stability; synchrotron radiation
Settore CHIM/03 - Chimica Generale e Inorganica
Settore CHIM/02 - Chimica Fisica
2023
3-feb-2023
Article (author)
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/955142
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