Insertion of Oxygen and Nitrogen in the Siliceous Zeolite TON at High Pressure

Year: 2021

Authors: Santoro M., Morana M., Scelta D., Rouquette J., Dziubek K., Gorelli F.A., Bini R., Garbarino G., Van Der Lee A., Di Renzo F., Coasne B., Haines J.

Autors Affiliation: Istituto Nazionale di Ottica, CNR-INO, Sesto Fiorentino, 50019, Italy; European Laboratory for Non Linear Spectroscopy (LENS), Sesto Fiorentino, 50019, Italy; ICCOM-CNR, Institute of Chemistry of OrganoMetallic Compounds, National Research Council of Italy, Via Madonna del Piano 10, Firenze, Sesto Fiorentino, I-50019, Italy; Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego 8, Poznan, 61-614, Poland; ICGM, CNRS, University de Montpellier, ENSCM, Montpellier, 34095, France; Dipartimento di Chimica “”Ugo Schiff””, Universita di Firenze, Sesto Fiorentino, 50019, Italy; ESRF, Grenoble, 38000, ESRF, 38000 Grenoble, France; University Grenoble Alpes, CNRS, LIPhy, Grenoble, 38000, France

Abstract: The insertion of oxygen and nitrogen molecules in the one-dimensional (1D) pore system of the zeolite TON was studied at high pressure by vibrational spectroscopy, X-ray diffraction, and Monte Carlo (MC) molecular modeling. Rietveld refinements and MC modeling indicate that, on average, six diatomic molecules per unit cell enter the pores of the zeolite. This induces changes in compressibility and distortion related to the Cmc21-to-Pbn21 phase transition compared to the empty-pore material. The filling behavior with N2 and O2 under pressure is similar to that of argon, suggesting that the kinetic diameter, which is very close in these three systems, plays a major role. The orientation of the diatomic molecules appears to have a rather minor effect on filling occurring at a slightly higher pressure for N2, which has a larger kinetic diameter. Both inserted molecules, initially not showing any marked orientation, begin to exhibit a degree of orientational order above 2 GPa.


Volume: 125 (35)      Pages from: 19517  to: 19524

More Information: The authors acknowledge funding from the Italian Ministry of Education, Universities and Research, MIUR PRIN project ZAPPING, number 2015HK93L7. The authors also thank the Deep Carbon Observatory (DCO) initiative under the project Physics and Chemistry of Carbon at Extreme Conditions and the Ente Cassa di Risparmio di Firenze under the project Firenze Hydrolab 2. K.D. acknowledges the Polish Ministry of Science and Higher Education for financial support through the “Mobilnosc Plus” program. Some of the computations in this paper were performed using the Froggy platform of the GRICAD infrastructure (, which is supported by the Rhone-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 Agence Nationale de la Recherche.
KeyWords: Diatomic molecules; Filling behavior; High pressure; Orientational orderings; Oxygen and nitrogens; Per unit; Pore system; Siliceous zeolite
DOI: 10.1021/acs.jpcc.1c05083

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