Abstract

Zeolites exhibit an immense range of applications, such as those in the chemical industry, electronics and photonics among others. We used non-catalytic zeolites in an entirely new fashion. In fact, high pressure (0.5–26 GPa) chemical reactions of simple molecules in the pores of a pure SiO2 zeolite, silicalite were performed in the diamond anvil cell to obtain unique nano-composites with drastically modified properties. These materials were investigated using a combination of X-ray diffraction and optical spectroscopy. We will first show how silicalite can be easily filled by simple molecules at high pressures and how this filling deactivates pressure induced amorphization of the silica framework. We will then present a silicon carbonate phase synthesized by reacting silicalite and molecular CO2 that fills the nano-pores, at 18–26 GPa and 600–980 K; the resulting compound is slightly metastable at room pressure. On the other hand, a nano-composite, which is stable at room temperature and pressure, is obtained by photo-polymerizing ethylene at 0.5–1.5 GPa under UV (351–364 nm) irradiation in the channels of silicalite. The structure of this material is characterized by single polyethylene chains adapting very well to the confining channels, which significantly modifies the physical properties of the silicalite framework. These findings may pave the way to the high pressure synthesis of a unique generation of technological materials.

Highlights

  • Meso/micro-porous solids such as zeolites are complex materials exhibiting an impressive range of applications, including molecular sieve, gas storage, catalysis, electronics and photonics [1,2,3,4,5,6,7,8,9,10,11]

  • Structural stability of silicalite under pressure We have recently shown that the insertion of simple molecules such as Ar, CO2 and C2H4 in the channels of silicalite deactivates pressure induced amorphization (PIA) in this zeolite, up to at least 25 GPa [13, 22]

  • As an additional test of the chemical reaction and of the nature of the compound, we measured the X-ray diffraction (XRD) patterns on a mixed CO2/silicalite sample compressed to 21.4 GPa and heated to 723 K [21]

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Summary

Introduction

Meso/micro-porous solids such as zeolites are complex materials exhibiting an impressive range of applications, including molecular sieve, gas storage, catalysis, electronics and photonics [1,2,3,4,5,6,7,8,9,10,11]. We performed high pressure (0.5-26 GPa) chemical reactions of simple molecules on a sub-nanometer scale in the channels of a pure SiO2, zeolite, silicalite to obtain unique nano-composite materials with drastically modified physical and chemical properties. This material was investigated using a combination of X-. We will first briefly show how silicalite can be filled by simple molecules such as Ar, CO2 and C2H4, among others, from the fluid phases at high pressures, and how this efficient filling deactivates the well known pressure induced amorphization of the silica framework up to at least 25 GPa [13] These results characterize the overall structural stability of our ideal, chemical nanolaboratory: the silicalite nano-channel. The high frequency components of these carbonate structures fit fairly well to the ambient pressure extrapolated frequencies of peaks A and B, thereby showing that the reaction of confined CO2 with silicalite results in the formation of unidentate, bidentate and bridged carbonates, involving either one or two framework silicon atoms

B B confined ν bulk
Findings
Conclusions
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