Fuel purification, Lewis acid and aerobic oxidation catalysis performed by a microporous Co-BTT (BTT3− = 1,3,5-benzenetristetrazolate) framework having coordinatively unsaturated sites

Abstract

Two isostructural microporous metal-organic frameworks [Co(DMA) were synthesized under solvothermal conditions. The structures of both compounds were determined by single-crystal X-ray diffraction data. Each compound adopts a porous three-dimensional framework consisting of square-planar [M 4 Cl] 7+ (M 2+ ¼ Co, 1; Cd, 2) units interconnected by triangular tritopic BTT 3À bridging ligands to give an anionic (3,8)-connected ''Moravia'' net. Phase purity of the compounds was confirmed by X-ray powder diffraction (XRPD), IR spectroscopy, thermogravimetric (TG) and elemental analysis. TGA and temperature-dependent XRPD (TDXRPD) experiments indicate a moderate thermal stability up to 350 and 300 C, respectively. Guest exchange followed by heating led to microporous solids with coordinatively unsaturated metal sites. These unsaturated metal sites create opportunities in adsorptive and catalytic applications. These have been probed by the selective removal of sulfur compounds from fuel feeds as well as the catalytic ring opening of styrene oxide and the oxidation of several cycloalkanes and benzyl compounds.

Multifunctional metal–organic frameworks: from academia to industrial applications

“…220 Two patents have been recently filed by this company concerning a MOF compound and its preparation method (WO2013160683A1, filed in 2013), 221 and another method of MOFs manufacture resulting in high surface area compounds (WO2014114948A1, filed in 2014). [222][223][224][225][226][227][228][229][230][231] It is important to emphasize that the thermal stability of MOFs is usually limited to temperatures below 400 ºC, which somehow reduces their potential with respect to applications at high temperatures. Both thermal and chemical stability and efficiency/cost ratio are crucial when studying MOFs for catalytic purposes.…”

Crystalline central-metal transformation in metal-organic frameworks

“…Excluding the effects of ligands and geometries, research into isostructural MOFs is beneficial for determining the relationships between metal ions and the corresponding properties of MOFs (such as electrical conductivity [28]). Series of isostructural M-MOF-74 (M = Mg, Mn, Fe, Co, Ni, Cu, Zn) [29][30][31][32][33], M-BTT (M = Mn, Fe, Co, Ni, Cu or Cd) [34,35], M-HKUST-1 (M = Cr, Cu, Zn, Mo, or Ru) [36][37][38], and lanthanide MOFs [39,40] have been constructed, but it is still difficult to obtain isostructural MOFs via a self-assembly synthetic pathway [41]. This is because the conventional synthetic pathway is relatively time-consuming or it is often challenging to diversify central-metal nodes.…”

Synthesis, structures, and properties of Co(II) and Zn(II) coordination polymers based on 1,3‐dicarbo‐hydrazine benzene

“… In addition, Co II ‐based CPs and MOFs also have caught the attention of researchers because of their potential applications as catalysts in oxidation chemistry and as adsorbents for air separation. Consequently, the desire to design and develop CPs or MOFs with luminescent properties and catalytic activities has pushed us to carry out further research on Zn II and Co II .…”