Synthesis of 1D Polymer/Zeolite Nanocomposites under High Pressure

Year: 2016

Authors: Santoro M., Scelta D., Dziubek K., Ceppatelli M., Gorelli FA., Bini R., Garbarino G., Thibaud JM., Di Renzo F., Cambon O., Hermet P., Rouquette J., van der Lee A., Haines J.

Autors Affiliation: CNR INO, Ist Nazl Ott, I-50019 Sesto Fiorentino, Italy; European Lab Non Linear Spect LENS, I-50019 Sesto Fiorentino, Italy; CNR ICCOM, Ist Chim Composti Organometall, I-50019 Sesto Fiorentino, Italy;‎ Adam Mickiewicz Univ, Fac Chem, Umultowska 89b, PL-61614 Poznan, Poland; Univ Firenze, Dipartimento Chim, I-50019 Sesto Fiorentino, Italy; European Synchrotron Radiat Facil, F-38343 Grenoble, France; Univ Montpellier, Inst Charles Gerhardt Montpellier, UMR 5253, CNRS,ENSCM, F-34095 Montpellier 5, France;‎ Univ Montpellier, Inst Europeen Membranes Montpellier, UMR 5635, CNRS,ENSCM, F-34095 Montpellier 5, France

Abstract: Recently, simple carbon based polymers have been synthesized at high pressures in silicalite, a pure SiO2 zeolite with a 3D system of mutually interconnected microchannels. These protocols permitted otherwise unstable polymers to be stabilized and protected from the atmosphere and to obtain an entirely novel class of nanocomposites with modified physical properties. In these 3-D systems, channel interconnection may prevent ideal, isolated polymer chains to be obtained. In this work, the :high pressure (5-10 GPa) synthesis of two archetypal, linear polymers polyacetylene (PA) and polycarbonyl (pCO) in the 1D channel system of the pure SiO2 zeolite ZSM-22 (TON) has been performed. The two resulting nano composites PA/TON and pCO/TON are organic/inorganic composite materials, which are good candidates as highly directional semiconductors and high energy density materials, respectively. The synthesis was performed in diamond anvil cells, starting from dense C2H2 and CO, confined in ZSM-22, and the nanocomposites were recovered at ambient conditions. The monomer polymerization was proven by IR spectroscopy and synchrotron X-ray diffraction measurements. DFT calculations were performed in order to obtain insight about the configurations of the 1D embedded polymers.

Journal/Review: CHEMISTRY OF MATERIALS

Volume: 28 (11)      Pages from: 4065  to: 4071

KeyWords: SOLID-STATE POLYMERIZATION; CARBON-MONOXIDE; CRYSTAL-STRUCTURE; EPSILON-PHASE; CO; SILICA; REACTIVITY; ACETYLENE; DIOXIDE; GPA
DOI: 10.1021/acs.chemmater.6b01639

Citations: 28
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