Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

Abstract

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

Structural Engineering of Low‐Dimensional Metal–Organic Frameworks: Synthesis, Properties, and Applications

“…[286][287][288][289][290][291] The catalytic active sites of MOF-based materials are usually originated from their coordinatively unsaturated metal sites (CUSs), and functional organic linkers. [286][287][288][289][290][291] The catalytic active sites of MOF-based materials are usually originated from their coordinatively unsaturated metal sites (CUSs), and functional organic linkers.…”

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

“…The MOF promoted the aerobic oxidation of dibenzothiophenes to their corresponding sulfones . Although this method is feasible and effective, synthesis of new long‐chain ligands is sometimes tedious work, requiring many synthetic steps . Further, after the development of the proper synthetic conditions for the linker design, some can have limited solubility, and hence do not form MOFs despite intensive screening of various reaction conditions.…”

Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

“…Metal–organic frameworks (MOFs), also called porous coordination polymers (PCPs), are a class of porous materials commonly obtained by the facile hydrothermal or solvothermal reactions of metal ions and bridging organic ligands at relatively low temperatures . In the past two decades, extensive research has been devoted to developing new MOFs and to exploring their application potential in many fields, such as gas storage, separation, catalysis, sensing, and biomedicine . Early on, a handful of MOFs was found to show a low affinity toward water and a permanent porosity, and this class of hydrophobic MOFs later received increasing attention due to their potential for use in practical adsorption and separation processes, even under humid conditions or in water.…”