Strong Swelling and Symmetrization in Siliceous Zeolites due to Hydrogen Insertion at High Pressure - Institut Charles Gerhardt - Institut de Chimie Moléculaire et des Matériaux de Montpellier Accéder directement au contenu
Article Dans Une Revue Angewandte Chemie International Edition Année : 2024

Strong Swelling and Symmetrization in Siliceous Zeolites due to Hydrogen Insertion at High Pressure

Résumé

Hydrogen and helium saturate the 1D pore systems of the high‐silica (Si/Al>30) zeolites Theta‐One (TON), and Mobile‐Twelve (MTW) at high pressure based on x‐ray diffraction, Raman spectroscopy and Monte Carlo simulations. In TON, a strong 22 % volume increase occurs above 5 GPa with a transition from the collapsed P2$_1$ to a symmetrical, swelled Cmc2$_1$ form linked to an increase in H$_2$ content from 12 H$_2$/unit cell in the pores to 35 H$_2$/unit cell in the pores and in the framework of the material . No transition and continuous collapse of TON is observed in helium indicating that the mechanism of H$_2$ insertion is distinct from other fluids. The insertion of hydrogen in the larger pores of MTW results in a strong 11 % volume increase at 4.3 GPa with partial symmetrization followed by a second volume increase of 4.5 % at 7.5 GPa, corresponding to increases in hydrogen content from 43 to 67 and then to 93 H$_2$/unit cell. Flexible 1D siliceous zeolites have a very high H$_2$ capacity (1.5 and 1.7 H$_2$/SiO$_2$ unit for TON and MTW, respectively) due to H$_2$ insertion in the pores and the framework, in contrast to other atoms and molecules, thereby providing a mechanism for strong swelling.

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Matériaux
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Dates et versions

hal-04623146 , version 1 (25-06-2024)

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Mario Santoro, Jérôme Rouquette, Marco Fabbiani, Francesco Di Renzo, Benoît Coasne, et al.. Strong Swelling and Symmetrization in Siliceous Zeolites due to Hydrogen Insertion at High Pressure. Angewandte Chemie International Edition, In press, ⟨10.1002/anie.202406425⟩. ⟨hal-04623146⟩
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