Titanium Phosphonate Porous Materials Constructed from Dendritic Tetraphosphonates

Abstract

An organic-inorganic hybrid material, TPPhA-Ti, was constructed by non-hydrolytic condensation of a dendritic tetrakis-1,3,5,7-(4-phosphonatophenyl)adamantane precursor and titanium(IV) isopropoxide. One preparative pathway yielded insoluble materials with a Ti/P ratio of approximately 1 which was confirmed by a combination of FT-IR, TGA, and EDS measurements. N2 sorption experiments showed that TPPhA-Ti is a porous solid (micropores approximately 13 A; mesopores approximately 38 A) with a high surface area, approximately 550 m2 g(-1). The structure and morphology of the TPPhA-Ti as investigated by transmission and scanning electron microscopy showed a layered-type material. Additional X-ray diffraction data suggest a paracrystalline material; an optimization of possible molecular arrangements of TPPhA-Ti was simulated that was in agreement with the experimental data. A second preparative pathway yielded a Ti oxide-phosphonate with a Ti/P ratio of approximately 3.4. Both TEM and SEM revealed that hollow nanospheres were formed with diameters of approximately 180-300 nm.

Insights into mesoporous metal phosphonate hybrid materials for catalysis

“…Several tactics have been employed to create porosity in metal phosphonates. Adjustment of phosphonate linkers, generally involving inserting non-pillaring phosphonic/phosphoric groups, 42 extending the microscopic dimension and geometry of polyphosphonic bridging molecules, [43][44][45] and attaching a secondary functional group ,46 provide reasonable methods. Recently, template-free approaches including nanocrystal selfassembly and microemulsion based on that the preformed metal phosphonate nanoclusters or nanoparticles performed as building units are taken to prepare mesoporous metal phosphonate hybrid materials, wherein weak interactions among the building blocks, including atoms, molecules, and related secondary units are required to direct the assembly process.…”

meta‐Phosphonobenzoic Acid: A Rigid Heterobifunctional Precursor for the Design of Hybrid Materials

“…More recently, 3D hybrid materials were formed starting from the rigid 3,5-diphosphonophenylphosphonic acid, [13] BINOL-diphosphonic acid, [14] or a rigid dentritic tetraphosphonic acid. [15] In the last two cases, microporous materials were formed. Finally, the use of rigid heterobifunctional organic building blocks has been employed few times to form new hybrids.…”

Nanostructured Titania–Diphosphonate Hybrid Materials with a Porous Hierarchy

“…[13] The assembly of individual nanostructured particles of metal organophosphonate into hierarchical nanoarchitectures with complex shapes for multifunctionalization and their potential applications is still a challenge. In this work, we report on the preparation of nanostructured titania-diphosphonate material with a porous hierarchy, in which hydroxyethylidene groups were anchored in the titaniaphosphonate network.…”