Mesoporous Zirconium Phenylenesiliconate‐phosphonate Hybrids with Ordered Lamellar Nanostructures

Abstract

Novel ordered lamellar mesostructure pZrPS-2 was hydrothermally prepared by using zirconium propoxide and 4-(EtO)2OPC6H4Si(OEt)3 (pPPS-E), which was hydrolyzed to organic building units substituted with both siliconate and phosphonate groups, in the presence of Cn TAB and TMAOH. The pZrPS-2 materials were obtained at a Zr/PPS ratio of 2 or higher and the basal spacing was increased by using a longer-chain surfactant (n = 12-18). Removal of the occluded surfactants at 300 °C resulted in retention of the lamellar structure with negligible shrinkage of the interlayer distance. Nitrogen adsorption studies revealed the ordered mesoporous nature of pZrPS-2 with a pore diameter of approximately 2 to 3 nm. The lamellar structure is assumed to be composed of layers that include zirconia-based crystalline nanodomains and interlayer pillars mainly based on PPS units. Although lamellar structures with the same crystalline phase also formed when no surfactant was added or when the meta isomer of PPS was used, no mesoporous materials were obtained except pZrPS-2. A possible schematic model to elucidate these results is also proposed.

Further Understanding of the Reactivity Control of Bisphosphonates to a Metal Source for Fabricating Highly Ordered Mesoporous Films

“…There have been no papers on the successful synthesis of mesostructured metal phosphonates by using bisphosphonate compounds bridged with asymmetric organic groups. Only one study on a surfactant‐assisted synthesis by using an asymmetric compound like diethylphosphatophenyltriethoxysilane, (EtO) 2 OP‐C 6 H 4 ‐Si(OEt) 3 , has been found, but the reactivities of both ends (P−OEt and Si−OEt) of the molecule are quite different and thus it would be difficult to obtain highly ordered mesoporous materials. In the NMR spectra of the partially acidified bisphosphonate having amide groups (Figure S1 in the Supporting Information), we cannot assign all signals due to its asymmetric structure.…”

Analytical Understanding of the Materials Design with Well‐Described Shrinkages on Multiscale

“…In previous work, this tool have been used to show as light lattice shrinkage of a mesoporousz irconium phenylenesiliconatephosphonate (O 3 PC 6 H 4 SiO 3 )a ta round 500 8C. [64]…”

“…In addition, this kind of shrinking processes are accompanied with gradual mass loss, which can be identified by TGA. In previous work, this tool have been used to show a slight lattice shrinkage of a mesoporous zirconium phenylenesiliconatephosphonate (O 3 PC 6 H 4 SiO 3 ) at around 500 °C …”

Microsphere Assemblies via Phosphonate Monoester Coordination Chemistry

“…Phosphonate‐based MOFs are an emerging class of MOFs due to their increased chemical, hydrolytic and thermal stability . Their enhanced stability has led to the development of phosphonate MOFs for a wide range of applications, including gas capture and separation, catalysis, and proton conduction . The topology of phosphonate MOFs is difficult to predict as they contain an extra oxygen compared to their carboxylate counterparts, which leads to more possible protonation states and coordination modes.…”

“…[1] Their enhanced stability has led to the development of phosphonate MOFs for aw ide range of applications, including gas capture and separation, [2][3][4][5] catalysis, [6,7] and protonc onduction. Phosphonate-based MOFs are an emerging class of MOFs due to their increased chemical, hydrolytic and thermals tability.…”