Metal-organic frameworks (MOFs) represent the largest known class of porous crystalline materials ever synthesized. Their narrow pore windows and nearly unlimited structural and chemical features have made these materials of significant interest for membrane-based gas separations. In this comprehensive review, we discuss opportunities and challenges related to the formation of pure MOF films and mixed-matrix membranes (MMMs). Common and emerging separation applications are identified, and membrane transport theory for MOFs is described and contextualized relative to the governing principles that describe transport in polymers. Additionally, cross-cutting research opportunities using advanced metrologies and computational techniques are reviewed. To quantify membrane performance, we introduce a simple membrane performance score that has been tabulated for all of the literature data compiled in this review. These data are reported on upper bound plots, revealing classes of MOF materials that consistently demonstrate promising separation performance. Recommendations are provided with the intent of identifying the most promising materials and directions for the field in terms of fundamental science and eventual deployment of MOF materials for commercial membrane-based gas separations.

Metal-organic frameworks (MOFs) have been widely recognized as one of the most fascinating classes of materials from science and engineering perspectives, benefiting from their high porosity and well-defined and tailored structures and components at the atomic level. Although their intrinsic micropores endow size-selective capability and high surface area, etc., the narrow pores limit their applications toward diffusion-control and large-size species involved processes. In recent years, the construction of hierarchically porous MOFs (HP-MOFs), MOF-based hierarchically porous composites, and MOF-based hierarchically porous derivatives has captured widespread interest to extend the applications of conventional MOF-based materials. In this Review, the recent advances in the design, synthesis, and functional applications of MOF-based hierarchically porous materials are summarized. Their structural characters toward various applications, including catalysis, gas storage and separation, air filtration, sewage treatment, sensing and energy storage, have been demonstrated with typical reports. The comparison of HP-MOFs with traditional porous materials (e.g., zeolite, porous silica, carbons, metal oxides, and polymers), subsisting challenges, as well as future directions in this research field, are also indicated.

The secondary building unit (SBU) has been identified as a useful tool in the analysis of complex metal-organic frameworks (MOFs). We illustrate its applicability to rationalizing MOF crystal structures by analysis of nine new MOFs which have been characterized by single-crystal X-ray diffraction. Tetrahedral SBUs in Zn(ADC)(2).(HTEA)(2) (MOF-31), Cd(ATC).[Cd(H(2)O)(6)](H2O)(5) (MOF-32), and Zn(2)(ATB)(H2O).(H2O)(3)(DMF)(3) (MOF-33) are linked into diamond networks, while those of Ni(2)(ATC)(H(2)O)(4).(H2O)(4) (MOF-34) have the structure of the Al network in SrAl(2). Frameworks constructed from less symmetric tetrahedral SBUs have the Ga network of CaGa(2)O(4) as illustrated by Zn(2)(ATC).(C(2)H(5)OH)(2)(H2O)(2) (MOF-35) structure. Squares and tetrahedral SBUs in Zn(2)(MTB)(H2O)(2).(DMF)(6)(H2O)(5) (MOF-36) are linked into the PtS network, which is the simplest structure type known for the assembly of these shapes. The octahedral SBUs found in Zn(2)(NDC)(3).[(HTEA)(DEF)(ClBz)](2) (MOF-37) form the most common structure for linking octahedral shapes, namely, the boron network in CaB(6). New structure types for linking triangular and trigonal prismatic SBUs are found in Zn(3)O(BTC)(2).(HTEA)(2) (MOF-38) and Zn(3)O(HBTB)(2)(H2O).(DMF)(0.5)(H2O)(3) (MOF-39). The synthesis, crystal structure, and structure analysis using the SBU approach are presented for each MOF.

Composites incorporating two-dimensional nanostructures within polymeric matrices have potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of freestanding nanosheets has proved challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometre lateral dimensions and nanometre thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increase in the separation selectivity with pressure. As revealed by tomographic focused ion beam scanning electron microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared with isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.

Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedicarboxylate) with a cubic three-dimensional extended porous structure adsorbed hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. Inelastic neutron scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules indicates the presence of two well-defined binding sites (termed I and II), which we associate with hydrogen binding to zinc and the BDC linker, respectively. Preliminary studies on topologically similar isoreticular metal-organic framework-6 and -8 (IRMOF-6 and -8) having cyclobutylbenzene and naphthalene linkers, respectively, gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.

Metal-organic frameworks--a class of porous hybrid materials built from metal ions and organic bridges--have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m(2) g(-1)). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g(-1)) and carbon dioxide (2,315 mg g(-1))--gases of high importance in the contexts of clean energy and climate alteration, respectively--in excellent agreement with predictions from modelling.

A family of isoreticular chiral metal-organic frameworks (CMOFs) of the primitive cubic network topology was constructed from [Zn(4)(μ(4)-O)(O(2)CR)(6)] secondary building units and systematically elongated dicarboxylate struts that are derived from chiral Mn-Salen catalytic subunits. CMOFs 1-5 were synthesized by directly incorporating three different chiral Mn-Salen struts into the frameworks under solvothermal conditions, and they were characterized by a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, and (1)H NMR. Although the CMOFs 1 vs 2 and CMOFs 3 vs 4 pairs were constructed from the same building blocks, they exhibit two-fold interpenetrated or non-interpenetrated structures, respectively, depending on the steric sizes of the solvents that were used to grow the MOF crystals. For CMOF-5, only a three-fold interpenetrated structure was obtained due to the extreme length of the Mn-Salen-derived dicarboxylate strut. The open channel and pore sizes of the CMOF series vary systematically, owing to the tunable dicarboxylate struts and controllable interpenetration patterns. CMOFs 1-5 were shown to be highly effective catalysts for asymmetric epoxidation of a variety of unfunctionalized olefins with up to 92% ee. The rates of epoxidation reactions strongly depend on the CMOF open channel sizes, and the catalytic activities of CMOFs 2 and 4 approach that of a homogeneous control catalyst. These results suggest that, although the diffusion of bulky alkene and oxidant reagents can be a rate-limiting factor in MOF-catalyzed asymmetric reactions, the catalytic activity of the CMOFs with large open channels (such as CMOFs 2 and 4 in the present study) is limited by the intrinsic reactivity of the catalytic molecular building blocks. The CMOF catalysts are recyclable and reusable and retain their framework structures after epoxidation reactions. This work highlights the potential of generating highly effective heterogeneous asymmetric catalysts via direct incorporation of well-defined homogeneous catalysts into framework structures of MOFs.

The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal-organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm(3) cm(-3) at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm(3) cm(-3) under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm(3) cm(-3), and between 5 and 80 bar, 230 cm(3) cm(-3).

Core-shell structured ZIF-8@ZIF-67 crystals are well-designed and prepared through a seed-mediated growth method. After thermal treatment of ZIF-8@ZIF-67 crystals, we obtain selectively functionalized nanoporous hybrid carbon materials consisting of nitrogen-doped carbon (NC) as the cores and highly graphitic carbon (GC) as the shells. This is the first example of the integration of NC and GC in one particle at the nanometer level. Electrochemical data strongly demonstrate that this nanoporous hybrid carbon material integrates the advantageous properties of the individual NC and GC, exhibiting a distinguished specific capacitance (270 F·g(-1)) calculated from the galvanostatic charge-discharge curves at a current density of 2 A·g(-1). Our study not only bridges diverse carbon-based materials with infinite metal-organic frameworks but also opens a new avenue for artificially designed nanoarchitectures with target functionalities.

Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen (David) Nanyang Technol Univ, Sch Chem & Biomed Engn, Singapore 637459, Singapore.

Antibiotics and organic explosives are among the main organic pollutants in wastewater; their detection and removal are quite important but challenging. As a new class of porous materials, metal-organic frameworks (MOFs) are considered as a promising platform for the sensing and adsorption applications. In this work, guided by a topological design approach, two stable isostructural Zr(IV)-based MOFs, Zr6O4(OH)8(H2O)4(CTTA)8/3 (BUT-12, H3CTTA = 5'-(4-carboxyphenyl)-2',4',6'-trimethyl-[1,1':3',1″-terphenyl]-4,4″-dicarboxylic acid) and Zr6O4(OH)8(H2O)4(TTNA)8/3 (BUT-13, H3TTNA = 6,6',6″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid)) with the the-a topological structure constructed by D4h 8-connected Zr6 clusters and D3h 3-connected linkers were designed and synthesized. The two MOFs are highly porous with the Brunauer-Emmett-Teller surface area of 3387 and 3948 m(2) g(-1), respectively. Particularly, BUT-13 features one of the most porous water-stable MOFs reported so far. Interestingly, these MOFs represent excellent fluorescent properties, which can be efficiently quenched by trace amounts of nitrofurazone (NZF) and nitrofurantoin (NFT) antibiotics as well as 2,4,6-trinitrophenol (TNP) and 4-nitrophenol (4-NP) organic explosives in water solution. They are responsive to NZF and TNP at parts per billion (ppb) levels, which are among the best performing luminescent MOF-based sensing materials. Simultaneously, both MOFs also display high adsorption abilities toward these organic molecules. It was demonstrated that the adsorption plays an important role in the preconcentration of analytes, which can further increase the fluorescent quenching efficiency. These results indicate that BUT-12 and -13 are favorable materials for the simultaneous selective detection and removal of specific antibiotics and organic explosives from water, being potentially useful in monitoring water quality and treating wastewater.

The trade-off between physical adsorption capacity and selectivity of porous materials is a major barrier for efficient gas separation and purification through physisorption. We report control over pore chemistry and size in metal coordination networks with hexafluorosilicate and organic linkers for the purpose of preferential binding and orderly assembly of acetylene molecules through cooperative host-guest and/or guest-guest interactions. The specific binding sites for acetylene are validated by modeling and neutron powder diffraction studies. The energies associated with these binding interactions afford high adsorption capacity (2.1 millimoles per gram at 0.025 bar) and selectivity (39.7 to 44.8) for acetylene at ambient conditions. Their efficiency for the separation of acetylene/ethylene mixtures is demonstrated by experimental breakthrough curves (0.73 millimoles per gram from a 1/99 mixture). Copyright © 2016, American Association for the Advancement of Science.

A series of five unique d-f heteronuclear luminescent metal-organic frameworks (MOFs) in an entangled polyrotaxane array and the light-harvesting block homonuclear zinc compound have been isolated successfully and characterized. The series of isostructural polymers feature 3,4-connected (4.8)(4.8.9)(6.8.9)(6.9)(8) topology and high stability, exhibiting diverse void spaces. By taking advantage of the isostructural MOFs 2 and 3, the intensities of red and green emissions can be modulated by adjusting the ratios of Eu and Tb ions correspondingly, and white-light emission can be generated by a combination of different doped Tb and Eu concentrations. The Tb-Zn-based framework {[TbZn(bipy)(Hmimda) (HO)]·5HO} (3; Hmimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid and bipy = 4,4'-bipyridine) can detect trace Mg ion with relatively high sensitivity and selectivity. Dehydrated MOF 3a shows a remarkable emission quenching effect through the introduction of I solids. Further investigation indicates that it exhibits turn on/off switchable properties for small solvent molecules or heavy-metal ions. Steady/transient-state near-IR luminescence properties for MOFs 1, 4, and 5 were investigated under visible-light excitation.

Chemodynamic therapy (CDT) can efficiently destroy tumor cells via Fenton reaction in the presence of HO and a robust catalyst. However, it has faced severe challenges including the limited amounts of HO and inefficiency of catalysts. Here, an adenosine triphosphate (ATP)-responsive autocatalytic Fenton nanosystem (GOx@ZIF@MPN), incorporated with glucose oxidase (GOx) in zeolitic imidazolate framework (ZIF) and then coated with metal polyphenol network (MPN), was designed and synthesized for tumor ablation with self-supplied HO and TA-mediated acceleration of Fe(III)/Fe(II) conversion. In the ATP-overexpressed tumor cells, the outer shell MPN of GOx@ZIF@MPN was degraded into Fe(III) and tannic acid (TA) and the internal GOx was exposed. Then, GOx reacted with the endogenous glucose to produce plenty of HO, and TA reduced Fe(III) to Fe(II), which is a much more vigorous catalyst for the Fenton reaction. Subsequently, self-produced HO was catalyzed by Fe(II) to generate highly toxic hydroxyl radical (•OH) and Fe(III). The produced Fe(III) with low catalytic activity was quickly reduced to reactive Fe(II) mediated by TA, forming an accelerated Fe(III)/Fe(II) conversion to guarantee efficient Fenton reaction-mediated CDT. This autocatalytic Fenton nanosystem might provide a good paradigm for effective tumor treatment.

The Fenton-like process presents one of the most promising strategies to generate reactive oxygen-containing radicals to deal with the ever-growing environmental pollution. However, developing improved catalysts with adequate activity and stability is still a long-term goal for practical application. Herein, we demonstrate single cobalt atoms anchored on porous N-doped graphene with dual reaction sites as highly reactive and stable Fenton-like catalysts for efficient catalytic oxidation of recalcitrant organics via activation of peroxymonosulfate (PMS). Our experiments and density functional theory (DFT) calculations show that the CoN site with a single Co atom serves as the active site with optimal binding energy for PMS activation, while the adjacent pyrrolic N site adsorbs organic molecules. The dual reaction sites greatly reduce the migration distance of the active singlet oxygen produced from PMS activation and thus improve the Fenton-like catalytic performance.

Using MIL-101(Fe) as the source of carbon and Fe, a magnetic porous carbon (MPC) material with FeC nanoparticles encapsulated in porous carbon was prepared through one-pot pyrolysis under N atmosphere. With MPC as adsorption material, a stir bar sorptive-dispersive microextraction (SBSDME) method was proposed to extract and preconcentrate sulfonamides (SAs) prior to HPLC-DAD determination. To investigate their extraction ability, different MPC materials were prepared under different carbonization temperatures (600, 700, 800, 900, and 1000 °C). The material prepared under 900 °C (MPC-900) exhibited the highest extraction ability for SAs. The as-prepared MPC materials were also characterized by Raman spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, zeta potential, and other techniques. The main parameters that affect extraction were systematically studied. Under optimal conditions, favorable linearity (R ≥ 0.9938) and detection limits (0.02-0.04 ng mL) of sulfonamides were obtained. The average recoveries for spiked milk and lake water samples ranged from 76.9 to 109% and from 75.4 to 118% with RSDs of 3.10-9.63% and 1.71-11.3%, respectively. Sulfameter and sulfisoxazole were detected in milk sample. Sulfisoxazole was detected in the lake water sample. The MPC-900 material demonstrated excellent reusability. It can be reused 24 times with peak areas having no obvious decline. The method can be applied to extract ultra-trace compounds in complex sample matrices. Schematic presentation of a stir bar sorptive-dispersive microextraction (SBSDME) by using magnetic porous carbon (MPC) composites as sorbent combined with high-performance liquid chromatography for sensitive analysis of sulfonamides in milk and lake water samples.© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.