Colloidal-Sized Metal–Organic Frameworks: Synthesis and Applications

Abstract

Colloidal metal-organic frameworks (CMOFs), nanoporous colloidal-sized crystals that are uniform in both size and polyhedral shape, are crystals composed of metal ions and organic bridging ligands, which can be used as building blocks for self-assembly in organic and aqueous liquids. They stand in contrast to conventional metal-organic frameworks (MOFs), which scientists normally study in the form of bulk crystalline powders. However, powder MOFs generally have random crystal size and shape and therefore do not possess either a definite mutual arrangement with adjacent particles or uniformity. CMOFs do have this quality, which can be important in vital uptake and release kinetics. In this Account, we present the diverse methods of synthesis, pore chemistry control, surface modification, and assembly techniques of CMOFs. In addition, we survey recent achievements and future applications in this emerging field. There is potential for a paradigm shift, away from using just bulk crystalline powders, towards using particles whose size and shape are regulated. The concept of colloidal MOFs takes into account that nanoporous MOFs, conventionally prepared in the form of bulk crystalline powders with random crystal size, shape, and orientation, may also form colloidal-sized objects with uniform size and morphology. Furthermore, the traditional MOF functions that depend on porosity present additional control over those MOF functions that depend on pore interactions. They also can enable controlled spatial arrangements between neighboring particles. To begin, we discuss progress regarding synthesis of MOF nano- and microcrystals whose crystal size and shape are well regulated. Next, we review the methods to modify the surfaces with dye molecules and polymers. Dyes are useful when seeking to observe nonluminescent CMOFs in situ by optical microscopy, while polymers are useful to tune their interparticle interactions. Third, we discuss criteria to assess the stability of CMOFs for various applications. In another section of this Account, we give examples of supracrystal assembly in liquid, on substrates, at interfaces, and under external electric fields. We end this Account with discussion of possible future developments, both conceptual and technological.

Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water

“…Furthermore, it has been indicated that ZIF-67's isostructure ZIF-8 exhibited structural instability under a highly acidic environment (i.e., soaked in a solution at pH = 1 for 24 h) (Sindoro et al, 2013). Nevertheless, the typical pH range of wastewater and aquacultural wastewater is from 4 to 9, and the adsorption time proposed in this study (i.e., 2 h) is relatively short.…”

Tuning optical properties of MOF-based thin films by changing the ligands of MOFs

“…These are crystalline materials consisting of metal ions or clusters and organic linker(s) with strong covalent bonds [6,7]. Due to their high porosity, large internal surface area, and high thermal stability (generally >300°C) [7], MOFs have a variety of potential applications in many fields including gas storage [8], catalysis [9,10], drug delivery [11], and chemical sensing [12][13][14].…”

Understanding the Colloidal Stability of the Mesoporous MIL-100(Fe) Nanoparticles in Physiological Media

“…1 Among them, an emerging class of nanoparticles is the nanometric porous metal organic frameworks (nanoMOFs), 2−4 whose unique tunable nature enables one to address the highly demanding set of requirements for their application in this field. 5 In this sense, one can select their composition (cation and organic linker) and type of porous architecture that render nanoMOFs both nontoxic and biodegradable and useful to load and deliver active molecules. 6 Their high and regular porosity combined with an internal amphiphilic microenvironment, well adapted to host a wide range of therapeutic guests, leads to exceptionally high payloads and a controlled release of the entrapped drugs under simulated physiological conditions.…”