The first part of this presentation will be devoted to the description of the two nanoporous crystalline forms and of the various co-crystalline structures which can be obtained with syndiotactic polystyrene (s-PS). Then, the second part will deal with the co-crystals formed with active guest molecules (nonlinear active, fluorescent, photoreactive, chiral, ...) while the final part of the lecture will focus on the possible applications of materials characterized by nanoporous crystalline s-PS phases.

Atomic layer deposition (ALD) has been used to coat SBA-15 and functionalized SBA-15 with various metal oxides. Use of SBA-15 coated with 4-10 ALD cycles of titania, alumina, niobia, or zirconia in the acid-catalyzed dehydration of fructose to 5-hydroxymethylfurfural (HMF) resulted in 24-57% conversion, with 0-22% selectivity, at 130 °C with 2 wt % fructose in 4:1 THF:H2O. Propylsulfonic acid functionalized SBA-15 (SBA-15-PrSO3H) had a 25% conversion and 48% selectivity for HMF under the same conditions. SBA-15-PrSO3H was also coated with 2 ALD cycles of titania followed by 8 ALD cycles silica. The deactivation rate constant for SBA-15-PrSO3H was 2.7 x 10-2 h-1 for the dehydration of fructose to HMF in a flow reactor at 130 °C with a feed of 2 wt % fructose in 4:1 THF:H2O. In comparison, the deactivation rate constant for the ALD coated SBA-15-PrSO3H-ALD was 7.9 x 10-3 h-1.

Metal organic framework (MOF) materials are a class of hybrid organic-inorganic crystalline materials whose pore structures and chemical properties can be tailored by the selection of component chemical moieties. Many MOFs have extraordinary intrinsic surface areas, capable of adsorbing large quantities of other chemicals, such as volatile organic compounds or moisture. Upon absorption of guest molecules, many MOFs undergo reversible changes in the dimensions of their unit cells. These properties suggest several routes to chemical sensing in which the transduction mechanisms are: 1) the stress induced at an interface between a flexible MOF layer and a static microcantilever fabricated with a built-in piezoresistive stress sensor; 2) the change in the resonant frequency of an oscillating microcantilever induced by mass adsorption; and 3) the change in the resonant frequency of a acoustic sensor, such as a surface acoustic wave (SAW) sensor through changes in mass loading and film moduli. This paper focuses on humidity sensing by SAWs coated with Cu3(BTC)2 (HKUST-1) over a very broad concentration range.

Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

As a part of a systematic study on cation-exchanged MOF-74-M, we report a partial snapshot of our recent work achieved via a fully periodic first principle approach. Structures are reported for bulk MOF-74-Mg, Mn, Ni, and Zn as computed at DFT-B3LYP level of theory; enthalpies of adsorption for CO and CO2 in interaction with MOF-74-Ni, and Zn are also investigated as obtained at B3LYP+D* level, which is able to take into account the long-range dispersion interaction between adsorbate and adsorbant, through an a-posteriori scheme. Results are discussed and compared with available experimental data. To the authors’ knowledge this represents the first description of MOF-74-Mn structure and of the interaction of the mentioned molecules with MOF-74-Zn.

The sodium in synthetic faujasite, commercial zeolite-X, was exchanged with copper cations at room temperature. A maximum number of 70 out of 86 Na cations were replaced with 35 copper cations (1). The copper exchanged zeolite was divided in six equal parts. Five of them were calcined at 43, 73, 112, 150 and 195 deg C. After calcination the samples were eluted with saturated solution of ammonium chloride to remove copper cations from open sites (super-cages) of the zeolite (Fig 1). The remaining copper cations were in locked sites (sodalite-cages or hexagonal-prisms). Using XAS edge-jump as a measure of quantitative analysis, we found that 9.0, 11.5, 12.7, 13.3 and 20.0 copper cations were locked at calcination temperatures of 43, 73, 112, 150 and 195 deg C respectively. The analysis of the first shell Fourier Transformed radial distribution shows that cations at site I in the hexagonal-prism and site I ‘ and II ’ in the sodalite-cages, adjacent to site I, are distributed at equal proportion, independent of temperature.