Functional Metal-organic Frameworks Research Articles

First-principles investigation of dimethyl-functionalized MIL-53(Al) metal–organic framework for adsorption and separation of xylene isomers

Functionalization of organic linker in metal–organic frameworks (MOFs) has been a popular method to utilize the porous material for a wide range of applications. In xylene separation, dimethyl functionalization of MOFs had demonstrated improved adsorptions properties. However, the effect of different xylene isomers on the organic linker is still not fully understood. In this work, the MIL-53(Al) MOF was functionalized with two methyl groups in ortho-, meta- and para-positions. The energy and thermochemical properties of xylene isomers when complexed dimethyl functionalized MIL-53(Al) MOFs were investigated using semiempirical quantum chemical PM6 method. The adsorption model of xylene isomers over meta-dimethyl-MIL-53(Al) (MDM) produced the lowest energy and the most thermochemically stable complex. The electronic properties, natural charge, nuclear magnetic resonance, aromaticity and molecular electrostatic potential of MDM complexes were further characterized using density functional theory (DFT) calculations at B3LYP/6-31G(d) level. DFT calculations revealed that the complex of MDM with m-xylene had the lowest adsorption energy and the highest reactivity, caused by the oxygen atoms surrounding the Al metal ion. In contrast, the complex of MDM with o-xylene had the highest energy of adsorption and the lowest reactivity, mostly governed by weak π interactions. Based on the results, we propose the use of MDM MOF for adsorption and separation of xylene isomers.

BODIPY functional metal–organic-frameworks for efficient visible-light-driven water oxidation without additional photosensitizers

BODIPY functional Fe-based MOFs exhibit excellent photocatalytic water oxidation activity without additional photosensitizers.

Copper nanoparticle anchored biguanidine-modified Zr-UiO-66 MOFs: a competent heterogeneous and reusable nanocatalyst in Buchwald-Hartwig and Ullmann type coupling reactions.

We have designed a functionalized metal–organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald–Hartwig C–N and Ullmann type C–O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.

Development of a pH-sensitive functionalized metal organic framework:in vitrostudy for simultaneous delivery of doxorubicin and cyclophosphamide in breast cancer

Exploration of an efficient dual-drug based nanocarrier with high drug loading capacity, specific targeting properties, and long-term stability is highly desirable in cancer therapy. Metal–organic frameworks (MOFs) have proven to be a promising class of drug carriers due to their high porosity, crystalline properties with defined structure information, and their potential for further functionalization. To enhance the drug efficacy as well as to overcome the burst effect of drugs, here we synthesized a pH responsive folic acid (FA) and graphene oxide (GO) decorated zeolitical imidazolate frameworks-8 (GO–FA/ZIF-8), for targeted delivery of doxorubicin (DOX) and cyclophosphamide (CP), simultaneously. In this system, DOX molecules were encapsulated in the pores of ZIF-8 during in situ synthesis of ZIF-8 and CP molecules have been captured by the GO surface via hydrogen bonding and π–π interactions as well. Furthermore, the resulting pH-responsive nanocarrier (DOX@ZIF-8/GO–FA/CP) showed in vitro sustained release characteristics (76% of DOX and 80% of CP) by cleavage of chemical bonding and disruption of the MOFs structure under acidic condition (at pH 5.6). Moreover, DOX@ZIF-8/GO–FA/CP has synergistic cytotoxic effects as compared to the combination of both the drugs without ZIF-8/GO–FA when treating MCF-7 and MDA-MB-231 breast cancer cell lines (with a combination index of 0.29 and 0.75 for MCF-7 and MDA-MB-231 cell-lines, respectively). Hence this system can be applied as an effective platform for smart dual drug delivery in breast cancer treatment through its remarkable manageable multidrug release.

A multifunctional colorimetric sensor originating from a cadmium naphthalene diimide-based metal–organic framework: photochromism, hydrochromism, and vapochromism

A new cadmium metal–organic framework with photocontrolled luminescence properties and multiple chromic properties was synthesized for used as a multifunctional colorimetric sensor and provide a new route to design functional MOFs.

Potassium Ions Induced Framework Interpenetration for Enhancing the Stability of Uranium-Based Porphyrin MOF with Visible-Light-Driven Photocatalytic Activity.

The stability of many MOFs is not satisfactory, which severely limits the exploration of their potential applications. Given this, we have proposed a strategy to improve the stability of MOFs by introducing alkali metal K+ capable of coordinating with metal nodes, which finally induces the interpenetrating uranyl-porphyrin framework to connect as a whole (IHEP-9). The stability experiments reveal that the IHEP-9 has good thermal stability up to 400 °C and can maintain its crystalline state in the aqueous solution with pH ranging from 2 to 11. The catalytic activity of IHEP-9 as a heterogeneous photocatalyst for CO2 cycloaddition under the driving of visible light at room temperature is also demonstrated. This induced interpenetration and fixation method may be promising for the fabrication of more functional MOFs with improved structural stability.

Metal Organic Frameworks (MOFs) as efficient carrier for targeted nanodrug delivery

A controllable and targeted drug delivery system development is imperative and important to reduce side effects and enhance the therapeutic efficacy of drugs. Metal-organic frameworks (MOFs), an emerging type of hybrid porous materials synthesized from metal ions or clusters abridged by organic linkers. They have attracted increasing attention in the recent years owing to the unique physical structures possessed, and the potential for wide range of applications. The superior properties of MOFs, such as well-defined pore aperture, tailorable composition and structure, tunable size, versatile functionality, high agent loading, and improved biocompatibility, have made them promising candidates as drug delivery hosts. MOFs for drug encapsulation and delivery is of great interest and many very promising results have been found, indicating that these porous solids exhibit several advantages over existing systems. This review highlights the recent advances in the synthesis, functionalization, and applications of MOFs in nanodrug delivery, and has classified them using drug loading strategies.

Ultra-High-Capacity Adsorption of Rhodamine B in a Carboxyl-Functionalized Metal–Organic Framework via Surface Adsorption

The adsorption of rhodamine B (RhB) from aqueous solution on a functionalized metal–organic framework UiO-66-(COOH)2 was studied systematically in view of the adsorption isotherm, kinetics, thermod...

Aggregology: Exploration and innovation at aggregate level

Aggregology: Exploration and innovation at aggregate level

(Invited) Three-Dimensional Nanostructuring of Metal-Organic Frameworks for Energy Applications

Metal-organic frameworks (MOFs) are a growing family of microporous materials that are attracting significant research and industrial interest, thanks to their unique features including a tuneable and narrow intrinsic pore size distribution, and very high surface area. MOFs are also being increasingly used as a precursor for the preparation of well-dispersed metal-containing carbon electrodes. A major challenge remains the three-dimensional structuring of MOFs into hierarchical functional morphologies and their integration as active elements in electrical material systems, due to their usually low electronic conductivities. Here, we present some flexible strategies for the structuring of MOFs into three-dimensional morphologies and their application for energy storage. In particular, we focus on lithium–sulfur (Li–S) batteries as a promising system for the next-generation of high energy density batteries. Despite progress, the energy density of current Li–S technologies is still below that of conventional intercalation-type cathode materials, due to limited stability and utilization efficiency at high sulfur loading.We demonstrate a highly performing free-standing monolithic electrode architecture for Li–S batteries with superior electrochemical stability and energy density [1]. The electrode layout consists of a highly conductive three-dimensional network of N,P co-doped carbon with well-dispersed metal-organic frameworks nano-domains of ZIF-67 and HKUST-1. The hierarchical monolithic 3D carbon networks provides an excellent environment for charge and electrolyte transport as well as mechanical and chemical stability. The electrically-integrated MOF nano-domains significantly enhance the sulfur loading and retention capabilities by inhibiting the release of lithium polysulfide specifies as well as improving the charge transfer efficiency at the electrolyte interface. Our optimal 3D carbon-HKUST-1 electrode architecture achieves a very high areal capacity of > 16 mAh cm−2 with a capacity retention of 82 % at 0.2C for over 300 cycles, providing an attractive candidate material for future high energy density Li–S batteries. We believe that our approaches provide some promising directions for the engineering of functional MOF morphologies for electrochemistry. References Liu, B.; Bo, R.; Taheri, M.; Di Bernardo, I.; Motta, N.; Chen, H.; Tsuzuki, T.; Yu, G.; Tricoli, A. Nano Lett. 2019, 19, (7), 4391-4399.

Electrochemically-assisted deposition of toluidine blue-functionalized metal-organic framework films for electrochemical immunosensing of Indole-3-acetic acid

A simple and rapid electrochemical synthesis strategy for in-situ fabrication of toluidine blue (TB)-functionalized metal organic framework ([email protected]) thin films via one-step reduction approach was reported. The [email protected] thin layer has been synthesized on the working electrode surface in different times at room temperature, and its morphology and thickness was characterized by varied instruments, including scanning electron microscope, transmission electron microscope, and scanning ion conductance microscope. The prepared [email protected] shows exceptional electrochemical activity and stability under mild conditions, and its electrochemical response is dependent on the amount of TB molecules which are encapsulated in the MOFs. Based on the [email protected] sensing platform, a sensitive label-free electrochemical immunosensor for the detection of Indole-3-acetic acid (IAA, a plant hormone) was developed with a wide linear range (2.5 pg mL−1 - 5 ng mL−1) and a low detection limit (1.4 pg mL−1). Moreover, this immune sensor shows good sensitivity and selectivity in real samples for IAA detection.

A Metal-Organic Framework Based on a Nickel Bis(dithiolene) Connector: Synthesis, Crystal Structure, and Application as an Electrochemical Glucose Sensor.

Functionalizing the redox-active tetrathiafulvalene (TTF) core with groups capable of coordination to metals provides new perspectives on the modulation of architectures and electronic properties of organic-inorganic hybrid materials. With a view to extending this concept, we have now synthesized nickel bis(dithiolene-dibenzoic acid), [Ni(C2S2(C6H4COOH)2)2], which can be considered as the inorganic analogue of the organic tetrathiafulvalene-tetrabenzoic acid (H4TTFTB). Likewise, [Ni(C2S2(C6H4COOH)2)2] is a redox-active linker for new functional metal-organic frameworks, as demonstrated here with the synthesis of [Mn2{Ni(C2S2(C6H4COO)2)2}(H2O)2]·2DMF, (1, DMF = N,N-dimethylformamide). 1 is isomorphic to the reported [Mn2(TTFTB)(H2O)2] (2) but is a better electrochemical glucose sensor due to the multiple oxidation-reduction states of the [NiS4] core, which allow glucose to be oxidized to glucolactone by the high oxidation state [NiS4] center. As a non-enzymatic glucose sensor, 1 on Cu foam (CF), 1-CF, was synthesized by a one-step hydrothermal method and exhibited an excellent electrochemical performance. The fabricated 1-CF electrode offers a high sensitivity of 27.9 A M-1 cm-2, with a wide linear detection range from 2.0 × 10-6 to 2.0 × 10-3 M, a low detection limit of 1.0 × 10-7 M (signal/noise = 3), and satisfactory stability and reproducibility.

Ambient CO2/N2 Switchable Pickering Emulsion Emulsified by TETA-Functionalized Metal-Organic Frameworks.

In recent years, metal-organic frameworks (MOFs) have been explored as emulsifiers for the fabrication of Pickering emulsions and then used for hybrid material synthesis and interface catalysis. Nevertheless, stimuli-responsive Pickering emulsions stabilized by MOFs have been rarely reported so far, although they are of great importance for fundamental research studies and practical applications. Herein, for the first time, triethylenetetramine (TETA)-functionalized MOFs (ZIF-90/TETA) have been designed, synthesized, and used for fabricating CO2-/N2-response Pickering emulsions. It is shown that even at the ZIF-90/TETA content of 0.25 wt %, the functional MOF can still efficiently emulsify n-hexane and water to form a high internal phase Pickering emulsion. Importantly, the Pickering emulsion can be easily and reversibly switched between emulsification and demulsification by bubbling of CO2 and N2 alternatively at atmospheric pressure. The possible mechanism of the CO2/N2 switchable emulsion is investigated by zeta potential, water contact angle, interfacial tension, 13C NMR spectroscopy, and an optical microscope. It is found that the acid-base reaction of CO2 with TETA anchored on the surface of ZIF-90 leads to the production of hydrophilic ammonium bicarbonate and carbamate, which results in the emulsification of the Pickering emulsion. However, when N2 is bubbled to remove CO2, the reverse reaction takes place to cause the demulsification of the Pickering emulsion. Moreover, the CO2/N2 switchable Pickering emulsion has been successfully used as a microreactor for Knoevenagel reactions to demonstrate a highly efficient integration of chemical reaction, product separation, and ZIF-90/TETA recycling for a sustainable chemical process.

One-step synthesis of functional metal organic framework composite for the highly efficient adsorption of tylosin from water

Functional metal organic framework composite can effectively remove antibiotics from environmental water samples. However, designing excellent adsorbents with multiple active sites via a rapid one-step method is still a challenging problem. A novel metal organic framework composite (UiO-66-NH2-AMPS) was synthesized through one-step polymerization by adding functional monomer 2-acrylamide-2-methylpropanesulfonic acid (AMPS) during the preparation of UiO-66-NH2. The microstructure and morphology of the UiO-66-NH2-AMPS composite were characterized, and the adsorption performance towards tylosin (TYL) in water was explored by equilibrium adsorption experiment. The results illustrated that the adsorption equilibrium can be reached within 1 h, and the maximum binding amount of UiO-66-NH2-AMPS for TYL was 161.60 mg g−1, which was approximately 2.1–329 times of that of the other adsorbents. The pseudo second-order kinetic and Liu isotherm model were suitable for the adsorption process, and thermodynamic study displayed that the adsorption of UiO-66-NH2-AMPS composite for TYL is spontaneous and endothermal. The infrared and X-ray photoelectron spectra exhibited that hydrogen bond and electrostatic interaction were the primary recognition force for TYL. The UiO-66-NH2-AMPS composite have been successfully applied to remove TYL from environmental water. After 5 cycles, the removal efficiency of UiO-66-NH2-AMPS was still above 91.30%.

Functionalized metal–organic frameworks with strong acidity and hydrophobicity as an efficient catalyst for the production of 5-hydroxymethylfurfural

Benzenesulfonic acid -functionalized MOF with hydrophobic network and high acid density is synthesized. • A benzenesulfonic acid-functionalized MOF is prepared. • The catalyst has a strong hydrophobic network and high acid density. • 98.0% yield of HMF is obtained in the dehydration of fructose. • The sulfonated metal–organic framework is stable for recycling. In the dehydration of fructose to 5-hydroxymethyl furfural (HMF), in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF, causing unsatisfactory catalytic activity and selectivity. In this work, a class of benzenesulfonic acid-grafted metal–organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent. The resultant MOFs have a specific surface area of greater than 250 m 2 ·g −1 , acid density above 1.0 mmol·g −1 , and water contact angle up to 129°. The hydrophobic MOF-PhSO 3 H exhibits both higher catalytic activity and selectivity than MOF-SO 3 H in the HMF synthesis due to its better hydrophobicity and olephilicity. Moreover, the catalyst has a high recycled stability. At last, fructose is completely converted, and 98.0% yield of HMF is obtained under 120 °C in a DMSO solvent system. The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.

Post‐Synthetic Modification of Metal–Organic Frameworks Toward Applications

AbstractPost‐synthetic modification (PSM) of metal–organic framework (MOF) compounds is a useful technique for preparing new MOFs that can exhibit or enhance many of the properties of the parent MOFs. PSM can be carried out by a number of approaches such as modifying the linker (ligand) and/or metal node, and adsorption/exchange of guest species. The surface environment of the MOF can be modified to increase structural stability as well as introducing desired properties. There is considerable scope in widening the applications of the MOF with compatible metal or ligand employing the PSM. This review focuses on the recent developments of modified materials through PSM, which augers well for the chemical modification and functionalization of MOFs. In this review, different types of PSM methods are presented in an orderly manner, and the diverse applications of resultant frameworks are described and discussed.

In Situ Growth of Tetrametallic FeCoMnNi-MOF-74 on Nickel Foam as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Oxygen and Hydrogen.

Multivariate metal-organic frameworks (MTV-MOFs) have drawn much attention in recent years for their promising applications in many fields of chemistry and materials. Constructing functional MOFs from multiple components for electrochemical water is crucial to high performance renewable energy storage and conversion devices. In this work, a series of bitmetallic-, trimetallic-, and tetrametallic-MOF-74/NFs were grown in situ on nickel foam (NF) by a facile solvothermal route. Specifically, the optimized FeCoMnNi-MOF-74/NF with a multilevel and hollow nanostructure was successfully fabricated and used as highly efficient bifunctional electrocatalysts for water splitting. It exhibited an ultralow overpotential of 250 and 108 mV to achieve the current density of 50 and 10 mA cm-2, along with the relatively small Tafel slope of 41.28 and 72.89 mV dec-1 for OER and HER in 1 M KOH, respectively. It is superior to other multimetallic-MOF-74 composites at the same condition and also surpasses the benchmark of commercial noble-metal catalysts as well. As a result, a low cell voltage of ca. 1.62 V was obtained at a current density of 10 mA cm-2, when tetrametallic FeCoMnNi-MOF-74/NF is employed as both anode and cathode electrodes for the real water splitting. The present work potentially provides a new insight into prospecting and designing multivariate MOFs as a promising material for efficient electrocatalysis in the practical application.

Metal-Organic Frameworks Based on Group 3 and 4 Metals.

Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status and future trends on the structural design of robust MOFs with high connectivity is provided. Cluster chemistry involving Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr is initially introduced. This is followed by a review of recently developed MOFs based on group 3 and 4 metals with their structures discussed based on the types of inorganic or organic building blocks. The novel properties and arising applications of these MOFs in catalysis, adsorption and separation, delivery, and sensing are highlighted. Overall, this review is expected to provide a timely summary on MOFs based on group 3 and 4 metals, which shall guide the future discovery and development of stable and functional MOFs for practical applications.

A nanozyme-linked immunosorbent assay based on metal–organic frameworks (MOFs) for sensitive detection of aflatoxin B1

In order to avoid the occurrence of false positives and false negatives caused by conventional enzyme-linked immunosorbent assay (ELISA), we established a novel indirect competitive MOF-linked immunosorbent assay (MOFLISA) method for the high throughput and high sensitive detection of aflatoxin B1. This method replaces the natural enzyme with functional MOFs to catalyze a chromogenic system. As a result, the limit of detection (LOD) of the MOFLISA method was 0.009 ng·mL−1 with a linear working range from 0.01 to 20 ng·mL−1. The developed MOFLISA method for AFB1 has a 20-fold improved LOD value compared with the conventional ELISA. The recoveries and relative standard deviations (RSD) ranged from 86.41 to 99.74% and 2.38–9.04%, respectively. The results demonstrate that the recovery rate and accuracy of this detection method is better than that of conventional ELISA, reducing risks offalsepositive andfalsenegativeresults.

A sunlight-responsive metal–organic framework system for sustainable water desalination

Light-responsive materials with high adsorption capacity and sunlight-triggered regenerability are highly desired for their low-cost and environmentally friendly industrial separation processes. Here we report a poly(spiropyran acrylate) (PSP) functionalized metal–organic framework (MOF) as a sunlight-regenerable ion adsorbent for sustainable water desalination. Under dark conditions, the zwitterionic isomer quickly adsorbs multiple cations and anions from water within 30 minutes, with high ion adsorption loadings of up to 2.88 mmol g−1 of NaCl. With sunlight illumination, the neutral isomer rapidly releases these adsorbed salts within 4 minutes. Single-column desalination experiments demonstrated that PSP–MOF works efficiently for water desalination. A freshwater yield of 139.5 l kg−1 d−1 and a low energy consumption of 0.11 Wh l−1 would be reached for desalinating 2,233 ppm synthetic brackish water. Importantly, this adsorbent shows excellent stability and cycling performance. This work opens up a new direction for designing stimuli-responsive materials for energy-efficient and sustainable desalination and water purification. Light-responsive smart materials hold promise for a solution to water desalination. Here the authors report an adsorbent based on a metal–organic framework that quickly adsorbs multiple ions from water in the dark, followed by release of these salts on exposure to sunlight.