Multicomponent Metal-organic Frameworks Research Articles

Precise selection and separation of ribavirin by nanoconfined imprinted MOFs membrane

Metal-organic frameworks (MOFs) are highly tunable materials with potential as porous media in membrane separations. However, traditional MOFs are usually not specific and selective. Here, we demonstrate a nanocomposite molecularly imprinted MOFs membrane material that can selectively adsorb and separate specific molecules. We demonstrated this adsorption-separation mechanism by introducing ribavirin molecules into multicomponent MOFs by molecular imprinting strategy and performing permeation and dynamic permeation tests. Due to the previously formed nanocages with a specific structure inside the MOFs, combined with the synergistic effect of the subsequent secondary imprinting, excellent selectivity (more than 6) and effective adsorption (46.46 mg g−1) were displayed by the obtained imprinted membrane. The stability of the membrane was measured by the process of dynamic osmosis, and the results showed that the membrane always had a large factor of separation (greater than 7). The experimental results and conclusions of this paper provide new theoretical and practical support for solving the key scientific issues of the “trade-off” effect between the permeation flux and permeation selectivity of template molecules in the traditional molecularly imprinted membranes (MIMs) osmotic separation process.

Yolk-Shell and Hollow Zr/Ce-UiO-66 for Manipulating Selectivity in Tandem Reactions and Photoreactions.

One of the hallmarks of multicomponent metal-organic frameworks (MOFs) is to finely tune their active centers to achieve product selectivity. In particular, obtaining bimetallic MOF hollow structures with precisely tailored redox centers under the same topology is still challenging despite a recent surge of such efforts. Herein, we present an engineering strategy named "cluster labilization" to generate hierarchically porous MOF composites with hollow structures and tunable active centers. By partially replacing zirconium with cerium in the hexanuclear clusters of UiO-66, unevenly distributed yolk-shell structures (YSS) were formed. Through acid treatment or annealing of the YSS precursor, single-shell hollow structures (SSHS) or double-shell hollow structures (DSHS) can be obtained, respectively. The active centers in SSHS and DSHS differ in their species, valence, and spatial locations. More importantly, YSS, SSHS, and DSHS with distinct active centers and microenvironments exhibit tunable catalytic activity, reversed selectivity, and high stability in the tandem reaction and the photoreaction.

Tuning and Directing Energy Transfer from the Blue to Near-Infrared Range in Multicomponent Metal-Organic Frameworks with seh Topology.

Luminescent metal-organic frameworks (MOFs) are emerging as one of several promising materials to study light-harvesting and energy-transfer processes. However, it is still a big challenge to tune and direct energy transfer in luminescent MOFs-based light-harvesting system. Herein, a series of new light-harvesting zinc-based luminescent MOFs with seh underlying topology were reported by successfully integrating 2,1,3-benzothiadiazole and its derivative-based carboxylic acids and pyridine-contained linkers into one structure. The strong spectra overlap between the emission and absorption spectra of carboxylic acids and pyridine-type linkers afforded an ideal platform to realize efficient energy transfer from the blue to near-infrared range. This work provides a novel approach to the rational design and synthesis of MOFs-based multicomponent light-harvesting materials with tunable energy transfer to mimic natural photosynthetic processes.

Polydopamine bridging strategy enables pseudomorphic transformation of multi-component MOFs into ultrasmall NiSe/WSe2@NC heterojunctions for enhanced alkaline hydrogen evolution

Heterojunction catalysts can synergistically promote the kinetics of energy-related reactions, but a significant challenge remains in fully exposing and engineering interfacial active sites. Herein, we developed a polydopamine (PDA) bridging strategy to construct multi-component metal-organic frameworks (MOFs) precursors to form ultrasmall NiSe/WSe2 @NC heterojunctions. Due to the ambiphilic binding of PDA to both NiMg-MOF and polyoxometalate (POM = H3PW12O40), subsequent selenization and MgO removal yield highly dispersed NiSe/WSe2 @NC with intimate heterointerfaces. By adjusting Mg2+ and POM loadings in PDA⊂NiMg-MOF-POM, the Ni:W:C ratios in NiSe/WSe2 @NC were fine-tuned, resulting in an optimized catalyst with low overpotential and high stability (21 mV at 10 mA·cm−2 for 60 h in 1.0 M KOH), rivaling the commercial 20% Pt/C (30 mV). X-ray absorption spectroscopy and density-functional theory calculations unveil that such “PDA bridging” strategy ensures highly exposed dual active centers and induced charge redistribution on heterointerface, resulting in accelerated water adsorption/dissociation and H2 evolution kinetics.

Stepwise construction of multi-component metal-organic frameworks.

Multi-component metal-organic frameworks (MC-MOFs) are crystalline porous materials containing multiple organic ligands or mixed metals, which manifest new properties beyond the linear combination of the single component. However, the traditional one-pot synthesis method for MOFs is not always applicable for synthesizing MC-MOFs due to the competitive coordination of multiple ligands and metals. Therefore, the stepwise construction of MC-MOFs has been explored, which enables more precise control of the heterogeneity within the ordered MC-MOFs. This review provides a summary of the synthesis strategies, namely, ligand exchange, coordinative modification, covalent modification, ligand metalation, cluster metalation, and use of mixed-metal precursors, for the stepwise construction of MC-MOFs. Furthermore, we discuss the applications of MC-MOFs with ordered arrangements of multiple functionalities, focusing on gas adsorption and separation, water remediation, heterogeneous catalysis, luminescence, and chemical sensing.

Partial Linker Substitution Strategy to Construct a Quaternary HKUST-like MOF for Efficient Acetylene Storage and Separation.

Multicomponent metal-organic frameworks (MOFs) have received much attention as emerging materials capable of precisely programing exquisite structures and specific functions. Here, we applied a partial linker substitution strategy to compile an HKUST-1-like quaternary MOF by introducing a bifunctional ligand into the well-known HKUST-1 structure. FUT-1, a new HKUST-like tbo topology MOF, was assembled with paddlewheel [Cu2(COO)4], triangular metallocycle pyrazole cluster Cu3(μ3-OH) (NN)3 building blocks, and two distinct linkers. FUT-1 exhibited good mechanical stability, water stability, and chemical stability (pH = 3-12) in aqueous solutions. Moreover, the porous environments created by this multicomponent primitive endow FUT-1 with high C2H2 storage and significantly selective separation performance of C2H2/CO2. Dynamic breakthrough experiments and ideal adsorbed solution theory calculations further demonstrate that FUT-1 can selectively capture C2H2 from C2H2/CO2 mixtures under ambient conditions. Based on grand canonical Monte Carlo simulations, the high C2H2 separation performance of FUT-1 is attributed to the π-complex formed between the C2H2 molecule and the trinuclear metallocycle clusters on the wall, which provides stronger affinity for C2H2 recognition than the CO2 molecule.

Tuning the Stereoselectivity of an Intramolecular Aldol Reaction by Precisely Modifying a Metal-Organic Framework Catalyst.

We report the catalysis of an enantioselective, intramolecular aldol reaction accelerated by an organocatalyst embedded in a series of multicomponent metal‐organic frameworks. By precisely programming the pore microenvironment around the site of catalysis, we show how important features of an intramolecular aldol reaction can be tuned, such as the substrate consumption, enantioselectivity, and degree of dehydration of the products. This tunability arises from non‐covalent interactions between the reaction participants and modulator groups that occupy positions in the framework remote from the catalytic site. Further, the catalytic moiety can be switched form one framework linker to another. Deliberately building up microenvironments that can influence the outcome of reaction processes in this way is not possible in conventional homogenous catalysts but is reminiscent of enzymes.

Mixed-Linker Isoreticular Zn(II) Metal-Organic Frameworks as Brønsted Acid-Base Bifunctional Catalysts for Knoevenagel Condensation Reactions.

Multicomponent metal-organic frameworks (MOFs) have received an increasing amount of attention due to their potential to produce new topologies, pore metrics, and functionalities compared to MOFs with a single metal cluster and one organic linker. Herein, five isoreticular Zn MOFs were obtained by mixing two types of linear ditopic linkers in a one-pot solvothermal synthesis. Interestingly, in the resulting Zn MOFs a six-connected cyclic trinuclear Zn(II) cluster and an eight-connected linear trinuclear Zn(II) cluster coexist, leading to an uncommon (6,8)-connected network. Catalytic activities toward the solvent-free Knoevenagel reactions were observed for all of these MOFs. Further experimental and computational studies suggest that they are Brønsted acid-base bifunctional catalysts. Through chemical modifications of dicarboxylate ligands, including their aromatic backbones and substituents, we have successfully implemented reticular chemistry for the modulations of pore sizes, surface areas, and catalytic performances in a series of four-component isoreticular MOFs.

Full-Color Emission in Multicomponent Metal–Organic Frameworks via Linker Installation

Herein, we demonstrate that linker installation (LI) through postsynthesis is an effective strategy to insert emissive second linkers into single-linker-based metal-organic frameworks (MOFs) to tune the emission properties of multicomponent MOFs. Full-color emission, including white-light emission, can be achieved via such a LI process.

Multicomponent metal-organic frameworks with aggregation-induced emission characteristics as fluorescence sensor array for the identification of energetic compounds

The identification of energetic compounds is of great importance in the field of national security and environmental monitoring. However, due to the continuous evolution of high energy density materials, the universal discrimination strategy for energetic compounds is still very challenging. Herein, a fluorescence sensor array consisting of multicomponent metal-organic frameworks with aggregation-induced emission (AIE) characteristics is developed for distinguishing three types of energetic compounds, including nitroaromatics, nitrogen-rich heterocycles, and nitramines. Through rational design of tetraphenylethene-based AIE linkers and co-ligands, as well as selection of metal nodes, the emissive AIE metal-organic frameworks can produce unique fluorescence quenching patterns corresponding to different energetic compounds in aqueous suspensions. Nine energetic compounds are discriminated within 5 orders of magnitudes ranging from 300 μM to 10 nM by principal component analysis. The resulting sensor array demonstrates excellent selectivity against a variety of interferences and is able to simultaneously distinguish inorganic improvised explosives, providing a new approach for designing olfactory-like sensing system.

Thermolabile Cross-Linkers for Templating Precise Multicomponent Metal-Organic Framework Pores.

While a number of approaches toward multicomponent metal-organic frameworks have been reported, new strategies affording greater structural versatility and molecular precision are needed to replicate the sophisticated active sites found in enzymes. Here, we outline a general method for templating functional groups within framework pores using thermolabile ligand cross-linkers. We show that tertiary ester-based cross-linkers can be used to install well-defined carboxylic acid pairs at precise relative distances and orientations. The tertiary ester linkages remain intact during framework formation but are readily cleaved to reveal free carboxylic acids upon microwave heating. Successful cross-linker synthesis, framework incorporation, and thermolysis is demonstrated using the mesoporous, terphenyl expanded analogues of MOF-74. When short cross-linkers are used, modeling studies show that the carboxylic acids are installed in a single configuration down the pore channels, spaced ∼7 Å apart. These precisely positioned acid pairs can be used as synthetic handles to build up more complex cooperative active sites.

A reticular chemistry guide for the design of periodic solids

Reticular chemistry — the linking of well-defined molecular building blocks by strong bonds into crystalline extended frameworks — has enabled the synthesis of diverse metal–organic frameworks (MOFs) and covalent organic frameworks, in which the pore shape, size and functionality can be tailored towards specific applications. Structural design methodologies are based on three main requisites: building blocks, targeted nets and isoreticular chemistry. In this Review, we highlight the well-developed and cutting-edge methodologies in reticular chemistry for the structural design and discovery of periodic solids. We illustrate the diversity of building blocks and delineate the suitable blueprint nets — namely, edge-transitive nets — for the design of MOFs. These edge-transitive nets are classified into three categories to help rationalize existing MOFs and to provide guidelines for the design of new structures. Two emerging topological concepts, namely, the merged-net approach and net-coded building units, are highlighted for their potential in synthesizing intricate or multi-component MOFs. We also consider isoreticular design strategies for the modification, expansion and contraction of building blocks, and identify challenges and opportunities in the assembly of increasingly intricate frameworks.

Probing Nonuniform Adsorption in Multicomponent Metal–Organic Frameworks via Segmental Dynamics by Solid-State Nuclear Magnetic Resonance

The guest adsorption phenomena in multicomponent metal-organic frameworks (MOFs) are intricate due to their structural complexities. In this work, we studied two members of the isostructural series of MUF-77 frameworks that consist of long or short alkyl groups. The adsorption of methanol, N,N-dimethylaniline (DMA) and acridine orange (AO) in two structures of MUF-77 has been investigated. 2H solid-state nuclear magnetic resonance (SSNMR) and two-dimensional 1H-13C NMR spectroscopy were used to probe the dynamics of various compartments of MUF-77. Through the analyses of dynamic behavior by SSNMR and molecular dynamics simulations, we elucidate the spatial distribution of guest molecules are nonuniform around different chemical components, in different pore structures, and across different parts of MOF lattice. In addition, we reveal that the framework flexibility of MUF-77 with short alkyl groups is reduced upon guest adsorption yet the framework flexibility of MUF-77 with long alkyl groups increases upon loading with methanol.

Stepwise Assembly of Turn‐on Fluorescence Sensors in Multicomponent Metal–Organic Frameworks for in Vitro Cyanide Detection

AbstractThe controlled synthesis of multicomponent metal–organic frameworks (MOFs) allows for the precise placement of multiple cooperative functional groups within a framework, leading to emergent synergistic effects. Herein, we demonstrate that turn‐on fluorescence sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. An anthracene‐based fluorescent linker and a hemicyanine‐containing CN−‐responsive linker were sequentially installed into the lattice of PCN‐700. The selective binding of CN− to hemicyanine inhibited the energy transfer between the two moieties, resulting in a fluorescence turn‐on effect. Taking advantage of the high tunability of the MOF platform, the ratio between anthracene and the hemicyanine moiety could be fine‐tuned in order to maximize the sensitivity of the overall framework. The optimized MOF‐sensor had a CN−‐detection limit of 0.05 μm, which is much lower than traditional CN− fluorescent sensors (about 0.2 μm).

Stepwise Assembly of Turn-on Fluorescence Sensors in Multicomponent Metal-Organic Frameworks for in Vitro Cyanide Detection.

The controlled synthesis of multicomponent metal-organic frameworks (MOFs) allows for the precise placement of multiple cooperative functional groups within a framework, leading to emergent synergistic effects. Herein, we demonstrate that turn-on fluorescence sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. An anthracene-based fluorescent linker and a hemicyanine-containing CN- -responsive linker were sequentially installed into the lattice of PCN-700. The selective binding of CN- to hemicyanine inhibited the energy transfer between the two moieties, resulting in a fluorescence turn-on effect. Taking advantage of the high tunability of the MOF platform, the ratio between anthracene and the hemicyanine moiety could be fine-tuned in order to maximize the sensitivity of the overall framework. The optimized MOF-sensor had a CN- -detection limit of 0.05 μm, which is much lower than traditional CN- fluorescent sensors (about 0.2 μm).

Multi-Spectroscopic Interrogation of the Spatial Linker Distribution in Defect-Engineered Metal-Organic Framework Crystals: The [Cu3 (btc)2-x (cydc)x ] Showcase.

In the past few years, defect‐engineered metal–organic frameworks (DEMOFs) have been studied due to the plethora of textural, catalytic, or magnetic properties that can be enhanced by carefully introducing defect sites into the crystal lattices of MOFs. In this work, the spatial distribution of two different non‐defective and defective linkers, namely 1,3,5‐benzenetricarboxylate (BTC) and 5‐cyano‐1,3‐benzenedicarboxylate (CYDC), respectively, has been studied in different DEMOF crystals of the HKUST‐1 topology. Raman micro‐spectroscopy revealed a nonhomogeneous distribution of defect sites within the [Cu3(btc)2−x(cydc)x] crystals, with the CYDC linker incorporated into defect‐rich or defect‐free areas of selected crystals. Additionally, advanced bulk techniques have shed light on the nature of the copper species, which is highly dynamic and directly affects the reactivity of the copper sites, as shown by probe molecule FTIR spectroscopy. Furthermore, electron microscopy revealed the effect of co‐crystallizing CYDC and BTC on the crystal size and the formation of mesopores, further corroborated by X‐ray scattering analysis. In this way we have demonstrated the necessity of utilizing micro‐spectroscopy along with a whole array of bulk spectroscopic techniques to fully describe multicomponent metal–organic frameworks.

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

AbstractThe resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three‐dimensional cubane‐1,4‐dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB‐30), comprising cdc, 4,4′‐biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.

Enhancing Multicomponent Metal-Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations.

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal-organic frameworks (MOFs) that contain the three-dimensional cubane-1,4-dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB-30), comprising cdc, 4,4'-biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π-π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.

Mimic of Ferroalloy To Develop a Bifunctional Fe-Organic Framework Platform for Enhanced Gas Sorption and Efficient Oxygen Evolution Electrocatalysis.

It is well-known that the formation of ferroalloy with the addition of the second or third metal during the steel-making process usually can improve the performance of the iron. Inspired by ferroalloy materials, it is speculated that the pore environment, framework charge, and catalytic properties of metal-organic frameworks (MOFs) could be optimized dramatically via the introduction of ferroalloy-like inorganic building blocks. However, different to ferroalloy, the accurate integration of different metals into one MOF platform is still challenging. Herein, taking advantages of the good compatibility for metals in trigonal prismatic trinuclear cluster, a series of Fe-based alloy-like [M3O(O2C)6] motifs (M3 = Fe3, Fe1.5Ni1.5, Fe1.5Co1.5, Fe1.5Ti1.5, FeCoNi, and FeTiCo) are successfully generated, which further lead to a robust Fe-MOF material family (SNNU-5s). These multicomponent MOFs not only provide a good chance to explore the impact of pore environment on gas adsorption/separation but also offer an opportunity to the efficient electrocatalytic reaction directly. Accordingly, compared with the SNNU-5-Fe parent structure, the pore characters of heterometallic SNNU-5 MOFs are clearly regulated by the type of alloy-like building blocks. SNNU-5-FeTi displays more superior gas separation performance for CO2/CH4, C2H2/CH4, C2H4/CH4, and C2H2/CO2 gas mixtures. What is more, benefited from the multimetallic active sites and their catalytic synergy, FeCoNi-ternary alloy-like cluster-based SNNU-5 MOF material exhibits an exceptional oxygen evolution reaction activity in aqueous solution at pH = 13, which delivers a low overpotential (ηj=10 = 317 mV), a fast reaction kinetics (Tafel slope = 37 mV dec-1), and excellent catalytic stability. This facile multialloy-like building block strategy holds promise to accurately design and improve the performance of MOFs, as well as open an avenue to understand the related mechanisms.

Tritopic Triazatruxene Ligands for Multicomponent Metal-Organic Frameworks.

Multicomponent metal-organic frameworks (MOFs) are built up from multiple ligands that are geometrically distinct. These ligands occupy specific positions in the MOF lattice. Installing different functionalities at precise locations in the framework is an important step in making MOFs for specific applications. This can be achieved by designing functionalized ligands for multicomponent MOFs. Here, we report a simple synthetic procedure for a new tritopic triazatruxene based tricarboxylic acid, H3 tat. We show that this ligand can be symmetrically derivatized with various substituents on its nitrogen centres. We report a new isoreticular series of well-ordered quaternary MOFs based on these new triazatruxene ligands together with two linear carboxylate ligands and Zn4 O clusters. These MOFs are isostructural to the previously reported MUF-77 series and show similar high surface areas and large pore volumes. Furthermore, H-bonding between the NH sites of the incorporated triazatruxene ligands and guest molecules is employed to modify their fluorescence behavior.