High Pressure Polymerization in a Confined Space: Conjugated Chain/Zeolite Nanocomposites

Year: 2014

Authors: Scelta D., Ceppatelli M., Santoro M., Bini R., Gorelli F.A., Perucchi A., Mezouar M., Van der Lee A., Haines J.

Autors Affiliation: European Lab Non Linear Spect LENS, I-50019 Sesto Fiorentino, Italy; CNR, ICCOM, I-50019 Sesto Fiorentino, Italy; CNR, INO, I-50019 Sesto Fiorentino, Italy; Univ Firenze, Dipartimento Chim Ugo Schiff, I-50019 Sesto Fiorentino, Italy; Elettra Sincrotrone Trieste SCpA, I-34149 Basovizza, Italy; European Synchrotron Radiat Facil, F-38343 Grenoble, France; Univ Montpellier 2, CNRS, UMR 5635, Inst Europeen Membranes Montpellier, F-34095 Montpellier 5, France; Univ Montpellier 2, CNRS, UMR 5253, Inst Charles Gerhardt Montpellier,Equipe C2M, F-34095 Montpellier 5, France.

Abstract: Conducting polymers are, one of the most promising classes of materials for enabling technologies such as solar energy conversion, organic electronics, and opto-electronics. The text-book conducting polymer is polyacerylene, which is difficult to synthesize in the all-conjugated form and also reacts with atmospheric moisture. Zeolites, widely used in diverse fields, could provide the ideal microporous framework capable of driving the ordered polymerization of acetylene. Also, the embedded polymer would be chemically protected by the zeolite, resulting in a unique organic/inorganic, conducting nanocomposite. We polymerized acetylene in the channels of a noncatalytic, pure SiO2 zeolite, silicalite in a diamond anvil cell, using only high pressure (similar to 4 GPa) as the driving force. A unique nanocomposite was obtained and recovered at ambient pressure, made of conjugated chains embedded in the silicalite as determined by combining different techniques: IR spectroscopy, Raman spectroscopy and microscopy, and X-ray diffraction. We thus made the first step toward the synthesis of a new generation of conducting polymers embedded in nanostructured hosts and also added to the development of mechanochemistry in highly confined systems.

Journal/Review: CHEMISTRY OF MATERIALS

Volume: 26 (7)      Pages from: 2249  to: 2255

More Information: We are grateful to our collegues Samuele Fanetti and Marco Pagliai for their precious help in Raman data processing. We acknowledge the ESRF and Elettra for provision of beam time at ID27 and SISSI, respectively. We also thank the support from the European Union (European Laboratory for non Linear Spectroscopy (LENS) Contract G.A. No. 284464 LASERLABEUROPE), the Ente Cassa di Risparmio di Firenze, the Deep Carbon Observatory initiative (Grant from the Alfred P. Sloan Foundation for the project entitled Physics and Chemistry of Carbon at Extreme Conditions), and the Agence Nationale de la Recherche (Contract ANR-09-BLAN-0018-01). One of us, M.S., thanks the Pole Chimie Balard of Montpellier for having supported his research as an Invited Professor at the Institut Charles Gerhardt in 2013, in the framework of the Total chair.
KeyWords: Solid-state Polymerization; Thermal-expansion; Raman; Zeolites; Silica; Phase; Electronics; Acetylene; Dynamics
DOI: 10.1021/cm500061f

Citations: 46
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