•Luminescent behaviors of lanthanide MOFs are described.•Lanthanide MOFs for luminescence sensing and light-emitting are summarized.•Controllable syntheses of nano-MOFs for sensors are discussed.
...Metal-organic frameworks (MOFs) have been emerging as very important multifunctional hybrid materials due to their inherent advantages of organic linkers and inorganic metal ions, tunable porosity and diverse functionality. The combination of the intrinsic luminescent features of lanthanide ions together with the unique characteristics of MOFs provides a fascinating opportunity for designing novel luminescent MOF materials. In this review, we summarize our research progress on the design and construction of luminescent lanthanide MOFs, as well as their potential functions and applications on luminescent sensing and light-emitting.
Metal–organic frameworks (MOFs) are an intriguing type of crystalline porous materials that can be readily built from metal ions or clusters and organic linkers. Recently, MOF materials, featuring ...high surface areas, rich structural tunability, and functional pore surfaces, which can accommodate a variety of guest molecules as proton carriers and to systemically regulate the proton concentration and mobility within the available space, have attracted tremendous attention for their roles as solid electrolytes in fuel cells. Recent advances in MOFs as a versatile platform for proton conduction in the field of humidity condition proton‐conduction, anhydrous atmosphere proton‐conduction, single‐crystal proton‐conduction, and including MOF‐based membranes for fuel cells, are summarized and highlighted. Furthermore, the challenges, future trends, and prospects of MOF materials for solid electrolytes are also discussed.
Metal–organic frameworks have received widespread attention for their role as solid electrolytes in fuel cells. The rich structural tunability, functional pore surface, and the high surface areas of such materials offer tremendous chances to orderly accommodate a variety of proton carriers and to systemically regulate the proton concentration and mobility within the available spaces.
Conspectus Achieving high performance functional materials has been a long-term goal for scientists and engineers that can significantly promote science and technology development and thus benefit ...our society and human beings. As well-known porous materials, metal–organic frameworks (MOFs) are crystalline open frameworks made up of molecular building blocks linked by strong coordination bonds, affording pore space for storing and trapping guest molecules. In terms of porosity, MOFs outperform traditional porous materials including zeolites and activated carbon, showing exceptional porosity with internal surface area up to thousands of square meters per gram of sample and with periodic pore sizes ranging from sub-nanometer to nanometers. Numerous MOFs have been synthesized with potential applications ranging from storing gaseous fuels to separating intractable industrial gas mixtures, sensing physical and chemical stimulus, and transmitting protons for conduction. Compared to traditional porous materials, MOFs are distinguished for their exceptional capability for pore adjustment and interior modification through pore engineering, which have made them a preeminent platform for exploring functional materials with high performance. Rational combinations of rigid building units of different geometry and multibranched organic linkers have provided MOFs with diverse pore structures, ranging from spherical to cylindrical, slit, and tubular ones isolating or interconnecting in different directions, which can be optimized for high-capacity gas storage. Based on the isoreticular principle and building blocks approach in MOF chemistry, the pore adjustment of porous materials can be performed with exquisite precision, making them suitable to address industrially important gas separation. The large pore cavities in MOFs are readily available for encapsulation of different functional guest species, resulting in novel MOF composite materials with various functions. In this Account, we summarize our recent research progress on pore engineering to achieve high-performance MOF materials. We have been able to tune and optimize pore structures, immobilize specific functional sites, and incorporate guest species into target MOF materials for hydrogen storage, methane storage, light-hydrocarbon purification, and proton conduction, especially for various industrially important gas separations including acetylene removal and ethylene and propylene purification. By engineering the porosity and pore chemistry that endows MOFs with multiple functionalities, our research endeavors have brought about the customization of high-performance MOF materials for corresponding application scenarios.
We summarize our ongoing research endeavors to explore and discover porous MOFs for gas separation and purification.
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•Our ongoing research endeavors to explore and discover porous ...MOFs for gas separation and purification are summarized.•Some of our breakthroughs on porous MOFs for gas separation and purification are described.•Strategies for pore and function engineering are discussed.
As a new generation of porous materials, metal–organic frameworks (MOFs, also known as porous coordination polymers) have shown great promise for gas separation and purification because of their unique pore structures and surfaces for their differential recognition of small gas molecules. In this review article, we summarize our ongoing research endeavors to explore and discover microporous MOFs for gas separation and purification. We have developed several approaches to systematically tune the pores and to immobilize functional sites, including (1) the primitive cubic net of interpenetrated microporous MOFs from the self-assembly of the paddle-wheel clusters, M2(CO2)4 (M = Cu2+, Zn2+…), with two types of organic dicarboxylic acid and pillar bidentate linkers; (2) microporous mixed-metal–organic frameworks (M′MOFs) through the metallo-ligands, and (3) microporous MOFs with dual functionalities. Such efforts have enabled us to make some breakthroughs on microporous MOFs for gas separation and purification, as demonstrated in the gas chromatographic separation of hexane isomers, kinetic D2/H2 separation, acetylene/ethylene separation, carbon dioxide capture, C2H2/CO2 and C3H4/C3H6 separation. Our group is one of the first groups who have envisioned the practical promise of microporous MOFs for the industrial gas separation and examined their separation capacities and efficiency using the fixed-bed adsorption and/or breakthrough experiments. Some of the very important and representative examples of these microporous MOFs for diverse gas separation and purification are highlighted in this review.
Extraction of lithium ions from salt‐lake brines is very important to produce lithium compounds. Herein, we report a new approach to construct polystyrene sulfonate (PSS) threaded HKUST‐1 ...metal–organic framework (MOF) membranes through an in situ confinement conversion process. The resulting membrane PSS@HKUST‐1‐6.7, with unique anchored three‐dimensional sulfonate networks, shows a very high Li+ conductivity of 5.53×10−4 S cm−1 at 25 °C, 1.89×10−3 S cm−1 at 70 °C, and Li+ flux of 6.75 mol m−2 h−1, which are five orders higher than that of the pristine HKUST‐1 membrane. Attributed to the different size sieving effects and the affinity differences of the Li+, Na+, K+, and Mg2+ ions to the sulfonate groups, the PSS@HKUST‐1‐6.7 membrane exhibits ideal selectivities of 78, 99, and 10296 for Li+/Na+, Li+/K+, Li+/Mg2+ and real binary ion selectivities of 35, 67, and 1815, respectively, the highest ever reported among ionic conductors and Li+ extraction membranes.
Going separate‐Li: Intergrown and continuous HKUST‐1 membranes through which polystyrene sulfonate (PSS) has been threaded are constructed, giving rise to a three‐dimensional network of sulfonate groups. As a result of different binding affinities to sulfonate and size sieving effects, the membrane allows very fast and selective lithium‐ion transportation, and thus separation from other metal ions.
Discoveries of novel functional materials have played very important roles to the development of science and technologies and thus to benefit our daily life. Among the diverse materials, ...metal–organic framework (MOF) materials are rapidly emerging as a unique type of porous and organic/inorganic hybrid materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers, and can be straightforwardly characterized by various analytical methods. In terms of porosity, they are superior to other well-known porous materials such as zeolites and carbon materials; exhibiting extremely high porosity with surface area up to 7000 m2/g, tunable pore sizes, and metrics through the interplay of both organic and inorganic components with the pore sizes ranging from 3 to 100 Å, and lowest framework density down to 0.13 g/cm3. Such unique features have enabled metal–organic frameworks to exhibit great potentials for a broad range of applications in gas storage, gas separations, enantioselective separations, heterogeneous catalysis, chemical sensing and drug delivery. On the other hand, metal–organic frameworks can be also considered as organic/inorganic self-assembled hybrid materials, we can take advantages of the physical and chemical properties of both organic and inorganic components to develop their functional optical, photonic, and magnetic materials. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of different species of diverse functions, so a variety of functional MOF/composite materials can be readily synthesized. In this Account, we describe our recent research progress on pore and function engineering to develop functional MOF materials. We have been able to tune and optimize pore spaces, immobilize specific functional groups, and introduce chiral pore environments to target MOF materials for methane storage, light hydrocarbon separations, enantioselective recognitions, carbon dioxide capture, and separations. The intrinsic optical and photonic properties of metal ions and organic ligands, and guest molecules and/or ions can be collaboratively assembled and/or encapsulated into their frameworks, so we have realized a series of novel MOF materials as ratiometric luminescent thermometers, O2 sensors, white-light-emitting materials, nonlinear optical materials, two-photon pumped lasing materials, and two-photon responsive materials for 3D patterning and data storage. Thanks to the interplay of the dual functionalities of metal–organic frameworks (the inherent porosity, and the intrinsic physical and chemical properties of inorganic and organic building blocks and encapsulated guest species), our research efforts have led to the development of functional MOF materials beyond our initial imaginations.
The first microporous hydrogen-bonded organic framework with permanent porosity and exhibiting extraordinarily highly selective adsorptive separation of C2H2 and C2H4 at ambient temperature has been ...established.
Porous MOFs are recognized as promising adsorbents capable of offering potential solutions to the enduring challenges pertaining to the safe storage and efficient use of acetylene and methane, which ...are considered as cleaner fuels and strategic gases. This review summarized the status related to acetylene and methane storage in MOFs, including the development history, acetylene/methane adsorption mechanisms, structure–property correlations, and synthetic strategies for improving acetylene/methane adsorption properties.
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•Comprehensive review on the status of porous metal–organic frameworks for gas storage, particularly on acetylene and methane.•Highlights on some representative porous metal–organic frameworks with record gas storage capacities.•Pore engineering strategies to maximize gas storage capacities within porous metal–organic frameworks.
Methane and acetylene represent cleaner fuels, which are considered as ideal alternatives to fossil fuels. Due to low volumetric energy density at ambient conditions, it is highly desirable to develop porous materials such as metal–organic frameworks that exhibit good adsorption properties with respect to them. In this review, we firstly introduced the development history on the design and synthesis of porous metal–organic frameworks for acetylene and methane storage in which some representative examples were analyzed; and then we focused on discussing their adsorption mechanisms including the gas binding sites and gas-framework interactions. At last, some structure–property relationships and synthetic strategies for improving gas adsorption properties with respect to them were summarized.
Hydrogen-bonded organic framework (HOF)-based catalysts still remain unreported thus far due to their relatively weak stability. In the present work, a robust porous HOF (HOF-19) with a ...Brunauer–Emmett–Teller surface area of 685 m2 g–1 was reticulated from a cagelike building block, amino-substituted bis(tetraoxacalix2arene2triazine), depending on the hydrogen bonding with the help of π–π interactions. The postsynthetic metalation of HOF-19 with palladium acetate afforded a palladium(II)-containing heterogeneous catalyst with porous hydrogen-bonded structure retained, which exhibits excellent catalytic performance for the Suzuki–Miyaura coupling reaction with the high isolation yields (96–98%), prominent stability, and good selectivity. More importantly, by simple recrystallization, the catalytic activity of deactivated species can be recovered from the isolation yield 46% to 92% for 4-bromobenzonitrile conversion at the same conditions, revealing the great application potentials of HOF-based catalysts.
Metal−organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self‐assembled through the ...coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre‐designing or post‐synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.
Metal−organic frameworks, as an emerging type of solid crystalline materials, can be straightforwardly self‐assembled through the coordination of metal ions/clusters with organic linkers. The functions of MOFs can not only originate from their porosities, but can also be generated from metal ions/clusters, organic linkers/metalloligands, or a variety of guest species, making MOFs a highly versatile and tunable platform to develop multifunctional materials for their broad applications
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