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

1. INTRODUCTION Among the classes of highly porous materials, metalÀorganic frameworks (MOFs) are unparalleled in their degree of tunability and structural diversity as well as their range of chemical and physical properties. MOFs are extended crystalline structures wherein metal cations or clusters of cations (\" nodes \") are connected by multitopic organic \" strut \" or \" linker \" ions or molecules. The variety of metal ions, organic linkers, and structural motifs affords an essentially infinite number of possible combinations. 1 Furthermore, the possibility for postsynthetic modification adds an additional dimension to the synthetic variability. 2 Coupled with the growing library of experimentally determined structures, the potential to computationally predict, with good accuracy, affinities of guests for host frameworks points to the prospect of routinely predesigning frameworks to deliver desired properties. 3,4 MOFs are often compared to zeolites for their large internal surface areas, extensive porosity, and high degree of crystallinity. Correspondingly, MOFs and zeolites have been utilized for many of the same applications

Metal–Organic Framework Materials as Chemical Sensors

The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti3C2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. The availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenes allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. In this Review, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research. More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist. Highly electrically conductive MXenes show promise in electrical energy storage, electromagnetic interference shielding, electrocatalysis, plasmonics and other applications.

/pdf/2d-metal-carbides-and-nitrides-mxenes-for-energy-storage-4zg2z3wp7h.pdf

2D metal carbides and nitrides (MXenes) for energy storage

Handbook on the Physics and Chemistry of Rare Earths is a continuing series of books covering all aspects of rare earth science, including chemistry, life sciences, materials science, and physics The handbook emphasizes rare earth elements [Sc, Y and the lanthanides (La through Lu)] but, when relevant, information also is included about the closely related actinide elements The individual chapters are comprehensive, broad, up-to-date critical reviews written by highly experienced invited experts The series, which was started in 1978 by Professor Karl A Gschneidner, Jr, combines and integrates both the fundamentals and applications of these elements and now publishes two volumes a yearCovers all aspects of rare earth science, including chemistry, life sciences, materials science, and physicsIncludes contributions from highly experienced, invited expertsProvides comprehensive, up-to-date critical reviews of developments in the fieldCombines and integrates both the fundamentals and applications of rare earth elements

Handbook on the Physics and Chemistry of Rare Earths

Metal–Organic Frameworks for Separations

Luminescence stability is a critical consideration for applying phosphors in practical devices. In this work, we report two categories of double p-tert-butylthiacalix[4]arene (H4TC4A) capped clusters that exhibit characteristic lanthanide luminescence. Specifically, {[Ln4(μ4-OH)(TC4A)2(DMF)6(CH3OH)3(HCOO)Cl2]}·xCH3OH (Ln = Eu (1), Tb (2); x = 0–1) with square-planar [Ln4(μ4-OH)] cluster cores and {[Ln9(μ5-OH)2(μ3-OH)8(OCH3) (TC4A)2 (H2O)24Cl9]}·xDMF (Ln = Gd (3), Tb (4), Dy (5); x = 2–6) with hourglass-like [Ln9(μ5-OH)2(μ3-OH)8] cluster cores are synthesized and characterized. By comparing 2 and 4, we find that several critical luminescence properties (such as quantum efficiency and luminescence stabilities) depend directly on the cluster core structure. With the square-planar [Ln4(μ4-OH)] cluster cores, 2 demonstrates high quantum yield (∼65%) and excellent luminescence stability against moisture, high temperature, and UV-radiation. A white light-emitting diode (LED) with ultrahigh color quality is successfully fabricated by mixing 2 with commercial phosphors. These results imply that high quality phosphors might be achieved by exploiting the double thiacalix[4]arene-capping strategy, with an emphasis on the cluster core structure.

/pdf/achieving-stable-photoluminescence-by-double-thiacalix-4-2d48izjj.pdf

Achieving stable photoluminescence by double thiacalix[4]arene-capping: the lanthanide-oxo cluster core matters

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Achieving stable photoluminescence by double thiacalix[4]arene-capping: the lanthanide-oxo cluster core matters