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

Year: 2024

Authors: Santoro M., Rouquette J., Fabbiani M., di Renzo F., Coasne B., Dong WW., Glazyrin K., Haines J.

Autors Affiliation: Univ Montpellier, ICGM, CNRS, ENSCM, F-34293 Montpellier, France; CNR, Ist Nazl Ottica INO, I-50019 Sesto Fiorentino, Italy; European Lab Non Linear Spect LENS, I-50019 Sesto Fiorentino, Italy; Univ Grenoble Alpes, CNRS, LIPhy, F-38000 Grenoble, France; Inst Laue Langevin, F-38042 Grenoble, France; Deutsch Elektronen Synchrotron DESY, Notkestr 85, D-22607 Hamburg, Germany; Chinese Acad Sci, Inst High Energy Phys, Beijing Synchrotron Radiat Facil, Beijing 100049, Peoples R China.

Abstract: 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/SiO2 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.

Journal/Review: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

Volume: 63 (31)      Pages from:   to:

More Information: We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III using the P02.2 Extreme Conditions Beamline. Beamtime was allocated for proposals I-20190775EC and I-20220012EC. Calculations were performed using the Dahu platform of the GRICAD infrastructure (https://gricad.univ-grenoble-alpes.fr), which is supported by the Rhpne-Alpes region (GRANT CPER07-13 CIRA) and the Equip@Meso project (reference ANR-10-EQPX-29-01) of the programme Investissements d’Avenir supervised by the French Research Agency.
KeyWords: hydrogen; zeolites; high-pressure; X-ray diffraction; Monte Carlo simulation
DOI: 10.1002/anie.202406425

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