Metal-organic Framework Nanocrystals Research Articles

A Universal Strategy toward Ultrasmall Hollow Nanostructures with Remarkable Electrochemical Performance

AbstractA facile and versatile microwave‐assisted and shell‐confined Kirkendall diffusion strategy is used to fabricate ultrasmall hollow nanoparticles by modulating the growth and thermal conversion of metal–organic framework (MOF) nanocrystals on graphene. This method involves that the adsorption of microwave by graphene creates a high‐energy environment in a short time to decompose the in situ grown MOF nanocrystals into well‐dispersed uniform core–shell nanoparticles with ultrasmall size. Upon a shell‐confined Kirkendall diffusion process, hollow nanoparticles of multi‐metal oxides, phosphides, and sulfides with the diameter below 20 nm and shell thickness below 3 nm can be obtained for the first time. Ultrasmall hollow nanostructures such as Fe2O3 can promote much faster charge transport and expose more active sites as well as migrate the volume change stress more efficiently than the solid and large hollow counterparts, thus demonstrating remarkable lithium‐ion storage performance.

Synthesis, characterization, and high potential of 3D metal–organic framework (MOF) nanoparticles for curing with epoxy

In this study, the potential of microporous 3D metal–organic framework (MOF) for curing epoxy resin has been discussed. First, MIL-101 (Cr), a chromium based MOF, was synthesized under hydrothermal condition and then characterized by using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetric (TGA) measurements. Epoxy nanocomposites containing 0.1, 0.3 and 0.5 wt% of MOF nanocrystals were subsequently prepared and their curability was studied in terms of the universal dimensionless Cure Index (CI) criterion under nonisothermal differential scanning calorimetry (DSC). Based on calculations made on the basis of the CI, epoxy nanocomposites containing 0.1, 0.3, and 0.5 wt% of MOF were labeled Good and Excellent thanks to an enhanced chemical interaction between MOF and epoxy matrix, where the heat of cure in the system was surprisingly even higher than that of the neat epoxy. It was demonstrated that introduction of MOF into epoxy significantly improved the heat release during crosslinking process of epoxy, as indicated by a 63% rise in the enthalpy of cure at MOF loading of 0.1 wt%. Addition of thermally stable MOF nanomaterials to the epoxy resin improved thermal decomposition resistance of epoxy. Up to 0.3 wt% loading, the system revealed acceptable thermal stability at elevated temperature featured by more residue remained at the end of test, while sample containing 0.5 wt% MOF resisted against decomposition at early stages of degradation due to higher thermal stability of MOF with respect to epoxy resin.

Hierarchical Porous Carbon Arising from Metal-Organic Framework-Encapsulated Bacteria and Its Energy Storage Potential.

Hierarchical porous carbons (HPCs) hold great promise in energy-related applications owing to their excellent chemical stability and well-developed porous structures. Attention has been drawn toward developing new synthetic strategies and precursor materials that permit greater control over composition, size, morphology, and pore structure. There is a growing trend of employing metal-organic frameworks (MOFs) as HPC precursors as their highly customizable characteristics favor new HPC syntheses. In this article, we report a biomimetically grown bacterial-templated MOF synthesis where the bacteria not only facilitate the formation of MOF nanocrystals but also provide morphology and porosity control. The resultant HPCs show improved electrochemical capacity behavior compared to pristine MOF-derived HPCs. Considering the broad availability of bacteria and ease of their production, in addition to significantly improved MOF growth efficiency on bacterial templates, we believe that the bacterial-templated MOF is a promising strategy to produce a new generation of HPCs.

In-situ fabrication of nanoarchitectured MOF filter for water purification

Sulfate radical (SO4•−)-based advanced oxidation processes (SR-AOPs) hold great promise for water purification due to their strong oxidizing and high selectivity. Recently, metal-organic frameworks (MOFs) as catalysts for peroxymonosulfate (PMS) activation to generate SO4•− have shown a bright future. However, the intrinsic nature of powder MOF nanocrystals, such as brittleness and poor processability, largely disturb their large-scale applications in practical. Herein, we develop an in situ growth method to prepare MOF filters. ZIF-67 in situ growth on the polyacrylonitrile (PAN) fibers lead to the ZIF-67/PAN composite fibers with high loading (up to 50 wt %). The loading ZIF-67 can retain their morphology and structure, which is comparable with that of pristine ZIF-67 powder. The ZIF-67/PAN filter demonstrates a high efficiency for organic pollutants removal by PMS activation. Furthermore, through the fabrication of filtration device, the dynamic catalysis results show the ZIF-67/PAN filter is a promising material for water purification. This work provides a new method for applying MOFs-based functional materials to practical water remediation and other separation applications.

Synthesis of metal–organic framework nanocrystals immobilized with 3D flowerlike Cu–Bi-layered double hydroxides for iodine efficient removal

Abstract

Green Synthesis of Hierarchical Metal-Organic Framework/Wood Functional Composites with Superior Mechanical Properties.

The applicability of advanced composite materials with hierarchical structure that conjugate metal–organic frameworks (MOFs) with macroporous materials is commonly limited by their inferior mechanical properties. Here, a universal green synthesis method for the in situ growth of MOF nanocrystals within wood substrates is introduced. Nucleation sites for different types of MOFs are readily created by a sodium hydroxide treatment, which is demonstrated to be broadly applicable to different wood species. The resulting MOF/wood composite exhibits hierarchical porosity with 130 times larger specific surface area compared to native wood. Assessment of the CO2 adsorption capacity demonstrates the efficient utilization of the MOF loading along with similar adsorption ability to that of pure MOF. Compression and tensile tests reveal superior mechanical properties, which surpass those obtained for polymer substrates. The functionalization strategy offers a stable, sustainable, and scalable platform for the fabrication of multifunctional MOF/wood‐derived composites with potential applications in environmental‐ and energy‐related fields.

Superwetting Oil/Water Separation Membrane Constructed from In Situ Assembled Metal-Phenolic Networks and Metal-Organic Frameworks.

Superwetting membranes with opposite wettability to oil and water have drawn intense attention in recent years for oil/water separation. Superhydrophilic and underwater superoleophobic membranes have shown unique advantages in the efficient treatment of oily wastewater containing oil-in-water emulsions. Facile interfacial engineering and microstructural design of the hierarchical architectures and the hydrophilic chemistry is of significance but still challenging. In this study, a hydrophilic hierarchical hybrid layer derived from metal-phenolic network (MPN)/metal-organic framework (MOF) synergy is constructed on the membrane surface via a proposed coordination-directed alternating assembly strategy. The assembly of MPN multilayers provides a hydrophilic chemical basis, and the assembly of MOF nanocrystals provides a hierarchical structural basis. Notably, the coordination interfacial interaction enables the formation of well-defined hydrophilic hierarchical architectures. The obtained membrane is thus endowed with robust superhydrophilicity, underwater superoleophobicity, and anti-oil-adhesion capability, which make it capable of highly efficient oil-water separation with high water permeance (above 6300 L/m2 h), high oil rejection (above 99.4%), and recyclable antifouling property. The high performance of the developed superwetting membrane makes it a competitive candidate for oil/water separation. Additionally, the demonstrated MPN/MOF assembly strategy may offer new prospects for the facile and versatile design of other superwetting materials.

Tuning Metal-Organic Framework Nanocrystal Shape through Facet-Dependent Coordination.

We studied coordination-dependent surfactant binding on shaped MOF nanocrystals. Cetyltrimethylammonium bromide (CTAB) on the surface of ZIF-8 was used as a model system. Infrared spectroscopic analysis and molecular dynamics simulations reveal different coordination environments for Zn nodes on {100} and {110} facets, resulting in different CTAB adsorption. We found that we are able to fine-tune the ratio of {100} and {110} facets in the nanocrystals. We also observed that once the MOF nanocrystals are enclosed by pure {110} facets growth along the {100} facets is terminated because the MOF nanocrystal has no surface area for CTAB adsorption. Growth can then be reinitiated through the etching of these rhombic dodecahedral nanocrystals to form a small amount of undercoordinated sites. This work represents the first systematic study of the design principles underpinning the synthesis of shaped MOF nanocrystals.

Zirconium-Based Metal–Organic Framework Nanocomposites Containing Dimensionally Distinct Nanocarbons for Pseudocapacitors

Electrically conductive nanocomposites composed of a zirconium-based metal–organic framework (MOF) and nanocarbons are synthesized by in situ growth of MOF nanocrystals in the presence of graphene ...

Fabrication of Hollow CoP/TiOx Heterostructures for Enhanced Oxygen Evolution Reaction.

Transition-metal phosphides have flourished as promising candidates for oxygen evolution reaction (OER) electrocatalysts. Herein, it is demonstrated that the electrocatalytic OER performance of CoP can be greatly improved by constructing a hybrid CoP/TiOx heterostructure. The CoP/TiOx heterostructure is fabricated using metal-organic framework nanocrystals as templates, which leads to unique hollow structures and uniformly distributed CoP nanoparticles on TiOx . The strong interactions between CoP and TiOx in the CoP/TiOx heterostructure and the conductive nature of TiOx with Ti3+ sites endow the CoP-TiOx hybrid material with high OER activity comparable to the state-of-the-art IrO2 or RuO2 OER electrocatalysts. In combination with theoretical calculations, this work reveals that the formation of CoP/TiOx heterostructure can generate a pathway for facile electron transport and optimize the water adsorption energy, thus promoting the OER electrocatalysis.

Metal-Layer Assisted Growth of Ultralong Quasi-2D MOF Nanoarrays on Arbitrary Substrates for Accelerated Oxygen Evolution.

Controlled growth of metal-organic frameworks (MOFs) nanocrystals on requisite surfaces is highly desired for myriad applications related to catalysis, energy, and electronics. Here, this challenge is addressed by overlaying arbitrary surfaces with a thermally evaporated metal layer to enable the well-aligned growth of ultralong quasi-2D MOF nanoarrays comprising cobalt ions and thiophenedicarboxylate acids. This interfacial engineering approach allows preferred chelation of carboxyl groups in the ligands with the metal interlayers, thereby making possible the fabrication and patterning of MOF nanoarrays on substrates of any materials or morphologies. The MOF nanoarrays grown on porous metal scaffolds demonstrate high electrocatalytic capability for water oxidation, exhibiting a small overpotential of 270 mV at 10 mA cm-2 , or 317 mV at 50 mA cm-2 as well as negligible decay of performance within 30 h. The enhanced performance stems from the improved electron and ion transport in the hierarchical porous nanoarrays consisting of in situ formed oxyhydroxide nanosheets in the electrochemical processes. This approach for mediating the growth of MOF nanoarrays can serve as a promising platform for diverse applications.

Nanopatterned metal–organic framework electrodes with improved capacitive deionization properties for highly efficient water desalination

Metal–organic frameworks (MOFs) are a family of highly porous materials with great potential to replace the dominance of porous carbon materials for capacitive deionization (CDI) application. However, MOF particles cannot be directly applied to fabricate CDI electrodes without the support of polymeric binders, which would consequently lead to the formation of a pyknotic electrode structure with poorer electrical conductivity, and lower accessible surface area, limiting their further CDI application. Herein we report the preparation of free-standing MOF electrodes by patterning MOFs nanocrystals directly on carbon cloth scaffold. Through such binder-free preparation procedure, the nanopatterned MOF electrode showcases an improved electrical conductivity and accessible surface area, giving rise to a maximum desalination capacity of 21.3 mg g−1, which is higher than those of the reported MOF electrodes and many carbon-based electrodes. This work highlights the significance of binder-dree preparation procedure on the CDI performance of MOF-based electrodes, and holds great potential for practical CDI application.

Ionic liquid and spatially confined gold nanoparticles enhanced photoelectrochemical response of zinc-metal organic frameworks and immunosensing squamous cell carcinoma antigen

Metal-organic framework nanocrystal (Zn-MOF) was synthesized by using 3,3'-{(propane-1,3-diyl)bis[1-(4-carboxybenzyl)-1H-imidazol-3-ium]} hexafluorophosphate ionic liquid as the functional monomer and Zn2+ as the central metal ion under hydrothermal conditions. Spatially confined gold nanoparticles (Au-NP) were prepared by in-situ reduction of chloroauric acid in the nanopores of Zn-MOF using acetic acid as the reducing agent to fabricate Au-NP@Zn-MOF nanocomposites. Au-NPs@Zn-MOF was further functionalized with 1H-imidazolium-1,3-bis(2-aminoethyl)bromide ionic liquid (IBABr) to prepare IBABr-Au@Zn-MOF nanocomposites. All abovementioned nanomaterials were thoroughly characterized by TEM, SEM, XPS, FTIR, and nitrogen-adsorption surface area analysis. IBABr-Au@Zn-MOFnanocomposites were then deposited onto a glassy carbon electrode and used as the photoactive element to fabricate a label-free photoelectrochemical (PEC) immunosensor by immobilizing anti-squamous cell carcinoma antigen (anti-SCCA). The PEC sensing principle is based on the photocurrent decline due to the blocking effect of SCCA on the electron and mass transfer after binding SCCA to anti-SCCA. The photocurrent variation related to the specific recognition of SCCA shows a linear relationship to the logarithm of SCCA concentration in the range of 5.0 pg mL−1 to 15.0 ng mL−1. The detection limit is as low as 2.34 pg mL−1. Such a signal-off PEC immunosensor is highly selective, sensitive, stable, and reproducible towards SCCA detection. Its performance is comparable to enzyme-linked immunosorbent assay from the studies on clinical samples. This immunosensor is promising for the label-free determining SCCA in clinical human serum samples.

Three-Dimensional Nanoarchitecture of Carbon Nanotube-Interwoven Metal–Organic Frameworks for Capacitive Deionization of Saline Water

The exploration of a new family of materials with superior performance for capacitive deionization (CDI) compared to commercial activated carbons is of significant interest. In this work, a three-dimensional (3D) nanoarchitecture composed of metal-organic frameworks (MOFs) interwoven by carbon nanotubes (CNTs) has been synthesized by utilizing CNTs to bridge the neighboring MOF nanocrystals. The resulting MOF/CNT hybrid not only shows improved electrical conductivity and 3D hierarchical structure but also retains the high porosity of MOFs. Consequently, the MOF/CNT hybrid exhibits a high desalination capacity of 16.90 mg g, highlighting the potential of noncarbonized MOF-based materials as CDI electrodes.

Sorbents screening for post-combustion CO2 capture via combined temperature and pressure swing adsorption

Adsorption-based post-combustion CO2 capture is enjoying significant research attention due to its potential for significant reductions in energy penalty, cost and environmental impact. Recent sorbent development work has focussed on polyethyleneimine (PEI) and dry sorbents that exhibit attractively low regeneration energy requirements. The main objective of this study is to identify best suitable sorbent for the recently published swing adsorption reactor cluster (SARC) concept. The screening results of four sorbents indicated two PEI sorbents to be good candidates for SARC application: a PEI sorbent functionalized with 1,2-epoxybutane supported on silica (referred to as EB-PEI in the rest of the document) and a PEI sorbent supported on mesoporous silica containing confined metal organic framework nanocrystals (referred to as PEI-MOF in the rest of the document). High resolution single-component isotherms revealed substantial differences in adsorption capacity and optimal operating temperatures for the two PEI sorbents, and CO2 and H2O isotherm models were derived from this data. Subsequently, breakthrough experiments and lab-scale reactor tests showed that co-feeding of CO2 and H2O had no significant effect, allowing the single-component isotherm models to be safely used in large-scale reactor simulations. Such a reactor model was then employed to illustrate the effect of the sorbent adsorption characteristics on the efficiency of the novel swing adsorption reactor cluster, which combines pressure and temperature swings. The EB-PEI and PEI-MOF sorbents were compared to a previously published PEI sorbent with distinctly different adsorption behaviour and recommendations for future sorbent development work were made.

Electrically Conducting Nanocomposites of Carbon Nanotubes and Metal‐Organic Frameworks with Strong Interactions between the two Components

AbstractHighly integrated nanocomposites of Zr‐based metal‐organic frameworks (MOFs) of the UiO‐66 class and multi‐wall carbon nanotubes (MWCNTs) are prepared by direct crystallization of MOFs in the presence of CNTs. Powder samples with homogeneously distributed and strongly intergrown nanotubes and nanoparticles are obtained. Growth of the MOFs in the presence of CNTs deposited on glass slides yields open or compact coatings of the nanocomposites. The materials combine the high porosity and versatility of MOFs with the high electrical conductivities of CNTs. Upon increasing the amount of CNTs in the synthesis, the electrical conductivity shows a clear percolation behavior. Even with small amounts of CNTs, high conductivities are observed. SEM and TEM pictures show the strong intergrowth between the CNTs and the MOF nanoparticles. Crystallization times are shorter in the presence of CNTs, and CNTs run centrally through the MOF crystals. These facts indicate that the CNTs serve as heterogeneous nucleation centers for the formation of MOF nanocrystals. Sensing experiments performed on the coatings show significant changes in the electrical conductivities of the nanocomposite materials in the presence of different analytes, which are also discernable from the changes observed on bare CNTs. This is further proof for the close interaction between the components of the nanocomposites.

Selective Adsorption-Based Separation of Flue Gas and Natural Gas in Zirconium Metal-Organic Frameworks Nanocrystals.

Carbon capture from flue gas and natural gas offers a green path to construct a net-zero emissions economic system. Selective adsorption-based gas separation by employing metal-organic frameworks (MOFs) is regarded as a promising technology due to the advantages of simple processing, easy regeneration and high efficiency. We synthesized two Zirconium MOFs (UiO-66 and UiO-66-NH2) nanocrystals for selective capture and further removal of CO2 from flue gas and natural gas. In particular, UiO-66-NH2 nanocrystals have a smaller grain size, a large amount of defects, and pending –NH2 groups inside their pores which display effective CO2 selective adsorption abilities over CH4 and N2 with the theoretical separation factors of 20 and 7. This breakthrough experiment further verified the selective adsorption-based separation process of natural gas and flue gas. In one further step, we used the Monte Carlo simulation to investigate the optimized adsorption sites and energy of CO2, N2 and CH4 molecules in the gas mixture. The significantly large adsorption energy of CO2 (0.32 eV) over N2 (0.19 eV) and N2 (0.2 eV) may help us to reveal the selective adsorption mechanism.

Metal-Organic Framework Films and Their Potential Applications in Environmental Pollution Control.

Metal-organic frameworks (MOFs), an emerging class of porous hybrid inorganic-organic crystals, exhibit very important application prospects in gas storage and separation, heterogeneous catalysis, sensing, drug release, environmental decontamination, etc., due to their competitive advantages over other traditional porous materials (e.g., activated carbon and zeolite), including high surface areas, adjustable pore size, uniformly distributed metal centers, and tunable functionalities. However, MOF particles are usually difficult to be processed into application-specific devices because of their brittleness, insolubility, difficulty in molding, and low compatibility with other materials. It is an urgent need to shape MOF nanocrystals into various useful configurations by developing effective fabrication methods. Specifically, versatile functional MOF films with robustness and operation flexibility are highly desired. Although an increasing number of MOF films and their diverse applications have been demonstrated, this field is still at an emerging stage with challenging issues. In this Account, we describe our recent research progress on controllable synthesis of MOF films, highlighting postsynthetic polymerization, in situ interweaving, and solvent-free hot-pressing methods. Basically, two main synthesis concepts are involved, including incorporation of the performed MOF particles into polymer matrix and in situ growth of MOF coatings on surface. In MOF/polymer hybrid films, MOF nanocrystals were covalently linked by flexible polymer chains via graft copolymerization, interconnected by functional polymer chains via in situ polymerization, or adhered to polymer matrix via specific interactions at interface, consequently leading to a molecular-level homogeneous membrane or functional coating layer or foam. In these examples, the existence of polymer endows MOF films with favorable features of processability and flexibility, along with new functions. Moreover, we developed an in situ solvent-free hot-pressing method as a general approach for efficient fabrication of MOF coatings on various commercial substrates (e.g., cloth and metal foils), where metal ions or ligands were chemically bonded to the surface functional groups or metal sites at the early stage of nucleation and subsequently assembled into continuous, uniform, and stable MOF layers under confined conditions. We further extended it to a scalable manufacturing method, roll-to-roll production. MOF films severing as filters (MOFilters) have significant applications in air and water purification. They show high and stable performance in PM capture along with a low pressure drop, holding promise of application in both industrial and residential environments. Moreover, MOFilters can remove SO2 and O3 from air by adsorption and catalytic decomposition, respectively. Given the functional diversity of MOFs, mixed pollutants in solution could also be efficiently trapped by multifunctional MOF hollow tubes. We believe this Account will offer new insights for design and preparation of functional MOF films and coatings and accelerate the practical applications of MOFs.

Conductive Metal–Organic Frameworks Selectively Grown on Laser‐Scribed Graphene for Electrochemical Microsupercapacitors

AbstractConductive 2D metal–organic frameworks (MOFs) have merits beyond traditional MOFs for electrochemical applications, but reports on using MOFs as electrodes for electrochemical microsupercapacitors (MSCs) are practically non‐existent. In this work, a Ni‐catecholate‐based MOF (Ni‐CAT MOF) having good conductivity and exhibiting redox chemistry in the positive and negative voltage windows is developed. A novel process is developed to selectively grow the conductive Ni‐CAT MOF on 3D laser scribed graphene (LSG). The LSG with its superior wettability serves as a functional matrix‐current collector for the hybridization of conductive Ni‐CAT MOF nanocrystals. Impressively, MSCs fabricated using the hybrid LSG/Ni‐CAT MOF show significant improvement compared with MOF‐free LSG electrodes. Specifically, the LSG/Ni‐CAT MOF electrodes can deliver MSCs with a wide operating voltage (1.4 V), high areal capacitance (15.2 mF cm−2), energy density (4.1 µWh cm−2), power density (7 mW cm−2), good rate performance, and decent cycling stability. This work opens up an avenue for developing electrochemical microsupercapacitors using conductive MOF electrodes.

Synthesis of Soluble Metal Organic Framework Composites for Mixed Matrix Membranes.

A general, green, efficient, and easily scalable methodology has been developed to more effectively incorporate (disperse) metal-organic frameworks (MOFs) into polymer technologies via solid state synthesis of any MOF nanocrystals within soluble mesoporous polymers. The resulting solid hybrid materials (pellets) can be directly transformed into colloidal MOF polymeric suspensions (inks) by simple dissolution in organic solvents. The straightforward use of novel colloidal MOF polymeric inks as ultimate additive for mixed matrix membranes resulted in unprecedented snakeskin microstructure exhibiting outstanding selectivity for CO2 over N2 (>100) from post-combustion flue gas at very low and well-dispersed MOF nanocrystal concentrations ranging from 1 to 7 wt %. This novel methodology brings one of the most versatile routes yet reported to transform any MOF into more functional forms that can be directly integrated into any conventional polymer technology at the commercial scale.