The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O(1, cyclam = 1,4,8,11-tetraazacyclotetradecane) has been prepared by reaction of (VO3) -anions and {Cu(cyclam)} 2+ complexes in NaCl (aq) at pH 4.6-4.7, and characterized by elemental analyses, thermogravimetry, and X-ray diffraction techniques (powder, single-crystal). Compound 1 exhibits a POMOF-like supramolecular open-framework built up of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross-sections of. 10.4 × 8.8 Å 2 . The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane.Porous crystalline materials such as metal organic frameworks (MOFs) have attracted great attention due to their wide range of relevant applications. 1 These materials are constructed by coordination of metal ions or metalcontaining units (nodes) to organic bridging ligands (linkers) to form open crystalline frameworks with permanent porosity. This feature qualifies them as suitable candidates for gas storage and separation, ion exchange, host-guest chemistry, magnetism, biomedicine and catalysis. 2 However, the synthesis of MOFs usually requires harsh conditions (e.g. high temperature or pressure, prolonged reaction times, harmful solvents, etc.), and removal of guest molecules from their cavities often leads to the collapse of the porous structure when flexible linkers are used. In this context, the incorporation of rigid and voluminous species such as metal clusters could increase the overall robustness

Highlights  Sol-gel/Hidrothermal method is efficient for the immobilization of HPA on zirconia  The presence of the HPA leads to significant modifications on zirconia  Supported HPA on zirconia are suitable catalysts for esterification.  Leaching and the porosity blockage cause a reduction of the catalytic activity.

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Abstract:In this work, we describe a very simple approach to develop tailored mesoporosity in any nanostructured heteropolysalt with control over both the mesoporous volume and the pore size. This approach consisting in a treatment of the solid microporous precursor with a basic agent has been tested on the ammonium salt of the Keggin-type [PMo12O40] 3− heteropolyanion, and constitutes a novel procedure for the preparation of mesoporous solids with no precedents in the literature. The results obtained in this study allows for extracting two main conclusions: (i) The micro-and mesoporosity structures in the heteropolysalt nanoparticles are independent from each other; and (ii) The development of mesoporosity in the solid material must be related with a process of alkaline degradation within the core of the nanocrystals aggregating into the particles. These results afford additional valuable information to the model of porosity that is established for heteropolysalts at present.