Nanoarchitectured Metal Phosphates and Phosphonates: A New Material Horizon toward Emerging Applications

Abstract

Metal phosphate- and phosphonate-based nanoarchitectured materials offer a unique opportunity to design hierarchically porous nanomaterials consisting of interconnected micropores, mesopores, and macropores. Due to their strong affinity toward the metal centers, the phosphate and phosphonate moieties act as ligand sites/linkers to form a wide spectrum of nanoarchitectured materials. In this review, we have summarized the synthetic routes in designing key microporous and mesoporous phosphate and phosphonate molecular sieves. Designing novel nanoarchitectures of metal phosphate- and phosphonate-based microporous and mesoporous materials for catalysis, adsorption, optoelectronics, electrochemical cells, fuel cells, and biomedical applications will further enrich the chemistry of these porous solids in the future.

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

“…Despite the limited number of phosphonate MOFs reported in the literature they have already created diverse applications in proton conductivity, catalysis, magnetism etc., and they exhibit potential in forming future non‐toxic MOFs, which are suitable for biological and food chemistry applications . The recent interest in phosphonate MOFs have been summarized in several review articles , . One of the distinctive natures of phosphonic acid metal binding group is the rich structural diversity observed in this system , , .…”

Facile Synthesis of Nanoporous Transition Metal‐Based Phosphates for Oxygen Evolution Reaction

“…Due to the large affinity of metal cations for the phosphate groups, numerous metallophosphates have been synthesized by using suitable synthesis conditions. [11] Furthermore, the introduction of nanoscale porosity into these phosphate-based materials is particularly desirable to enhance their catalytic [12] and energy [13] applications. Among these open framework architectures, metal phosphates are very intriguing due to the unique properties associated with each of the metal atoms present in the frameworks.…”

A Semiconductive and Microporous One-Dimensional Tubular Metal-Organic Framework

“…Recently, two new families of MOFs have emerged, which employ phosphonic and phosphinic acids as metal-binding units, in contrast with the conventional MOFs that contain carboxylates and azolates. [25][26][27][28] Phosphonic acids are able to support extremely rich metal-binding modes, while phosphinic acids have carboxylate-like metal-binding modes. [28] The presence of d-orbitals in the phosphorus atom can give rise to rich electronic interactions, which have resulted in completely different geometries compared to those of conventional MOFs.…”

“…[28] The presence of d-orbitals in the phosphorus atom can give rise to rich electronic interactions, which have resulted in completely different geometries compared to those of conventional MOFs. [25][26][27][28] Owing to the higher strength of the C-P and P-O bonds compared to R-C=O bonds, phosphonate MOFs exhibit higher thermal and chemical stabilities compared to conventional MOFs. [12,29,30] To the best of our knowledge, the total number of microporous phosphonate MOFs is currently less than 0.001% of the total number of reported MOFs.…”

“…Due to the rich metal-binding modes of organophosphonates, the rational synthesis of phosphonate MOFs into predefined one-, two-, and three-dimensional frameworks has been a great challenge. [25][26][27] Previously, phosphonate monoesters mimicking the carboxylate metal binding were used to generate microporous MOFs. [35,36] Recently, we developed a new strategy to retain monodeprotonated R-PO3H -1 in hydrothermal reactions via a pH-controlled synthesis.…”