Organoamine Templated Multifunctional Hybrid Metal Phosphonate Frameworks: Promising Candidates for Tailoring Electrochemical Behaviors and Size-Selective Efficient Heterogeneous Lewis Acid Catalysis.

Abstract

The successful discovery of novel multifunctional metal phosphonate framework materials that incorporate newer organoamines and their utilization as a potential electroactive material for energy storage applications (supercapacitors) and as efficient heterogeneous catalysts are the most enduring challenges at present. From this perspective, herein, four new inorganic-organic hybrid zinc organodiphosphonate materials, namely, [C5H14N2]2[Zn6(hedp)4] (I), [C5H14N2]0.5[Zn3(Hhedp) (hedp)]·2H2O (II), [C6H16N2][Zn3(hedp)2] (III), and [C10H24N4][Zn6(Hhedp)2(hedp)2] (IV) (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid), have been synthesized through the introduction of different organoamines and then structurally analyzed using various techniques. The compounds (I-IV) possess a three-dimensional network through alternate connectivity of zinc ions and diphosphonate ligands, as confirmed using single-crystal X-ray diffraction. The investigations of electrochemical charge storage behaviors of the present compounds indicate that compound III exhibits a high specific capacitance of 190 F g-1 (76 C g-1) at 1 A g-1, while compound II shows an excellent cycling stability of 90.11% even after 5000 cycles at 5 A g-1 in the 6 M KOH solution. Further, the present materials have also been utilized as active heterogeneous Lewis acid catalysts in the ketalization reaction. The screening of various substrate scopes during the catalytic process confirms the size-selective heterogeneous catalytic nature of the framework compounds. To our utmost knowledge, such a size-selective heterogeneous Lewis acid catalytic behavior has been observed for the first time in the amine templated inorganic-organic hybrid framework family. Moreover, the excellent size-selective catalytic efficiencies with the d10 metal system and recyclability performances make the compounds (I-IV) more efficient and promising Lewis acid heterogeneous catalysts.