Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Selective gas adsorption and separation in metal–organic frameworks

Metal–Organic Frameworks for Separations

Cause, conseguenze e strategie di mitigazione Proponiamo il primo di una serie di articoli in cui affronteremo l’attuale problema dei mutamenti climatici. Presentiamo il documento redatto, votato e pubblicato dall’Ipcc - Comitato intergovernativo sui cambiamenti climatici - che illustra la sintesi delle ricerche svolte su questo tema rilevante.

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Climate Change 2007: The Physical Science Basis.

Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites.

Metal–organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas A very interesting and well-investigated topic is their optical emission properties and related applications Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011 This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection

Luminescent metal–organic frameworks for chemical sensing and explosive detection

Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are open, crystalline supramolecular coordination architectures with porous facets. These chemically tailorable framework materials are the subject of intense and expansive research, and are particularly relevant in the fields of sensory materials and device engineering. As the subfield of MOF-based sensing has developed, many diverse chemical functionalities have been carefully and rationally implanted into the coordination nanospace of MOF materials. MOFs with widely varied fluorometric sensing properties have been developed using the design principles of crystal engineering and structure–property correlations, resulting in a large and rapidly growing body of literature. This work has led to advancements in a number of crucial sensing domains, including biomolecules, environmental toxins, explosives, ionic species, and many others. Furthermore, new classes of MOF sensory materials utilizing advanced signal transduction by devices based on MOF photonic crystals and thin films have been developed. This comprehensive review summarizes the topical developments in the field of luminescent MOF and MOF-based photonic crystals/thin film sensory materials.

Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.

Fluorescence-baseddetection is gaining increasing attention owing to its highsensitivity, simplicity, short response time, and its ability to beemployed both in solution and solid phase. Numerousp-electron-rich fluorescent conjugated polymers have beensynthesized, and are used in the detection of trace amounts ofnitro aromatics.

Highly selective detection of nitro explosives by a luminescent metal-organic framework.

A fluorescent metal–organic framework for highly selective detection of nitro explosives in the aqueous phase

The development of solid-state proton-conducting materials with high conductivity that operate under both anhydrous and humidified conditions is currently of great interest in fuel-cell technology. A 3D metal–organic framework (MOF) with acid–base pairs in its coordination space that efficiently conducts protons under both anhydrous and humid conditions has now been developed. The anhydrous proton conductivity for this MOF is among the highest values that have been reported for MOF materials, whereas its water-assisted proton conductivity is comparable to that of the organic polymer Nafion, which is currently used for practical applications. Unlike other MOFs, which conduct protons either under anhydrous or humid conditions, this compound should represent a considerable advance in the development of efficient solid-state proton-conducting materials that work under both anhydrous and humid conditions.

Two-in-one: inherent anhydrous and water-assisted high proton conduction in a 3D metal-organic framework.

Sugar-assisted stable monometallic nanoparticles were synthesized by wet chemical method following a general scheme. Judicious manipulation of the reducing capabilities of different sugars has shown to have a bearing on the particle size that corroborates the shift of the absorbance peak positions and TEM analysis. Evaporation of the precursor solutions on the solid surface (strong metal--support interaction), led to the formation of smaller particles. Under the experimental condition, spherical nanoparticles of approximately 1, 3, 10 and 20 nm sizes were prepared reproducibly for gold, platinum, silver and palladium, respectively. Fructose has been found to be the best suited sugar for the synthesis of smaller particles and remained stable for months together.

Sujit K. Ghosh

Papers

Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.

Highly selective detection of nitro explosives by a luminescent metal-organic framework.

A fluorescent metal–organic framework for highly selective detection of nitro explosives in the aqueous phase

Two-in-one: inherent anhydrous and water-assisted high proton conduction in a 3D metal-organic framework.

General method of synthesis for metal nanoparticles