Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal-Organic Frameworks.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin-lattice relaxation time (T1) is increased up to ∼60 µs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics.

Increasing the Accessibility of Internal Catalytic Sites in Covalent Organic Frameworks by Introducing a Bicontinuous Mesostructure.

Introducing continuous mesochannels into covalent organic frameworks (COFs) to increase the accessibility of their inner active sites has remained a major challenge. Here, we report the synthesis of COFs with an ordered bicontinuous mesostructure, via a block copolymer self-assembly-guided nanocasting strategy. Three different mesostructured COFs are synthesized, including two covalent triazine frameworks and one vinylene-linked COF. The new materials are endowed with a hierarchical meso/microporous architecture, in which the mesochannels exhibit an ordered shifted double diamond (SDD) topology. The hierarchically porous structure can enable efficient hole-electron separation and smooth mass transport to the deep internal of the COFs and consequently high accessibility of their active catalytic sites. Benefiting from this hierarchical structure, these COFs exhibit excellent performance in visible-light-driven catalytic NO removal with a high conversion percentage of up to 51.4 %, placing them one of the top reported NO-elimination photocatalysts. This study represents the first case of introducing a bicontinuous structure into COFs, which opens a new avenue for the synthesis of hierarchically porous COFs and for increasing the utilization degree of their internal active sites.

A General Synthesis of Nanostructured Conductive Metal-Organic Frameworks from Insulating MOF Precursors for Supercapacitors and Chemiresistive Sensors.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique subclass of layer-stacked crystalline coordination polymers that simultaneously possess porous and conductive properties, and have broad application potential in energy and electronic devices. However, to make the best use of the intrinsic electronic properties and structural features of 2D c-MOFs, the controlled synthesis of hierarchically nanostructured 2D c-MOFs with high crystallinity and customized morphologies is essential, which remains a great challenge. Herein, we present a template strategy to synthesize a library of 2D c-MOFs with controlled morphologies and dimensions via insulating MOFs-to-c-MOFs transformations. The resultant hierarchically nanostructured 2D c-MOFs feature intrinsic electrical conductivity and higher surface areas than the reported bulk-type 2D c-MOFs, which are beneficial for improved access to active sites and enhanced mass transport. As proof-of-concept applications, the hierarchically nanostructured 2D c-MOFs exhibit a superior performance for electrical properties related applications (hollow Cu-BHT nanocubes-based supercapacitor and Cu-HHB nanoflowers-based chemiresistive gas sensor), achieving over 225 % and 250 % improvement in specific capacity and response intensity over the corresponding bulk type c-MOFs, respectively.

Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers.

Conjugated coordination polymers (c-CPs) are unique organic-inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows for the modulation of the electronic structure of c-CPs while maintaining the structural topology. The redox-state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5-tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag4TTHQ and Ag4TTBQ (TTBQ=1,2,4,5-tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two-dimensional Ag-S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag4TTHQ and 0.5 eV for Ag4TTBQ) and conductivities (0.4 S/cm for Ag4TTHQ and 10 S/cm for Ag4TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag4TTHQ. Consequently, Ag4TTHQ displays a high Seebeck coefficient of 330 µV/K and a power factor of 10 µW/m ⋅ K2, surpassing Ag4TTBQ and the other reported silver-based c-CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm2/V ⋅ s in both Ag4TTHQ and Ag4TTBQ.

Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by "4 + 2" Phenyl Ligands.

Electrically conductive coordination polymers and metal-organic frameworks are attractive emerging electroactive materials for (opto-)electronics. However, developing semiconducting coordination polymers with high charge carrier mobility for devices remains a major challenge, urgently requiring the rational design of ligands and topological networks with desired electronic structures. Herein, we demonstrate a strategy for synthesizing high-mobility semiconducting conjugated coordination polymers (c-CPs) utilizing novel conjugated ligands with D2h symmetry, namely, "4 + 2" phenyl ligands. Compared with the conventional phenyl ligands with C6h symmetry, the reduced symmetry of the "4 + 2" ligands leads to anisotropic coordination in the formation of c-CPs. Consequently, we successfully achieve a single-crystalline three-dimensional (3D) c-CP Cu4DHTTB (DHTTB = 2,5-dihydroxy-1,3,4,6-tetrathiolbenzene), containing orthogonal ribbon-like π-d conjugated chains rather than 2D conjugated layers. DFT calculation suggests that the resulting Cu4DHTTB exhibits a small band gap (∼0.2 eV), strongly dispersive energy bands near the Fermi level with a low electron-hole reduced effective mass (∼0.2m0*). Furthermore, the four-probe method reveals a semiconducting behavior with a decent conductivity of 0.2 S/cm. Thermopower measurement suggests that it is a p-type semiconductor. Ultrafast terahertz photoconductivity measurements confirm Cu4DHTTB's semiconducting nature and demonstrate the Drude-type transport with high charge carrier mobilities up to 88 ± 15 cm2 V-1 s-1, outperforming the conductive 3D coordination polymers reported till date. This molecular design strategy for constructing high-mobility semiconducting c-CPs lays the foundation for achieving high-performance c-CP-based (opto-)electronics.

Nanoassembled Interface for Dynamics Tailoring.

The properties and performance of solid nanomaterials in heterogeneous chemical reactions are significantly influenced by the interface between the nanomaterial and environment. Oriented tailoring of interfacial dynamics, that is, modifying the shared boundary for mass and energy exchange has become a common goal for scientists. Although researchers have designed and constructed an abundance of nanomaterials with excellent performances for the tailoring of reaction dynamics, a complete understanding of the mechanism of nanomaterial-environment interfacial interaction still remains elusive. To predictively understand the nanomaterial-environment relationship over a wide range of time scale, a deep and dynamic insight is required urgently. In this Account, our recent works including advances in the design and construction of nanoassembled interfaces and understanding the dynamic interaction mechanisms between different combinations of nanoparticle (NP) assembly environment interfaces for tailoring the reaction dynamics.NP assemblies with well-defined structures and compositions are inherently suitable for replacing bulk-type nanomaterials for the research on interfaces. We primarily introduced two most relevant nanoassembled surfaces that were fabricated in our laboratory, namely, ordered self-assembly interface and animate nanoassembled interface. The disordered nanoparticles can be arranged into an ordered superlattice based on the self-assembly method and patterned-assembly method. In addition, we used NPs with flexible properties to construct three-dimensional (3D) animate assemblies. On the basis of a thorough understanding of the structure-property correlation, a series of nanoassembled interfaces with various structures have been developed for practice. In comparison with traditional nanomaterial-environment interfaces, the nanoassembled interfaces can change the mode of contact between the nanomaterial and environment, thereby maximizing the number of active sites and driving interferent/product off the nanoassembled interface. The geometry, porosity, and deformable/motional properties in the nanoassembled interface can be applied to enhance the mass transfer dynamics in the chemical reaction. Moreover, the nanoassembled interface can be used to strengthen the affinity between the NP assemblies and targets, thereby enhancing the adsorption efficiency. As shown in these examples, the nanoassembled interface can effectively change the speed, intensity, and mode of interactions between the NP assemblies and environment in spatiotemporal scales.The overall performance of the interfacial dynamics can be improved by the nanoassembled interface, thereby facilitating practical application in flowing systems. We have extended the applications of nanoassembled interfaces from simple adsorption to complex reactions in flowing systems, including in vivo magnetic resonance imaging, electrocatalytic gas evolution reaction, bacterial capture, sensing of exhaled volatile organic compounds, and heterogeneous catalysis. Our current endeavors to explore the applicability of animate nanoassembled interfaces for dynamic tailoring have widened the scope of research, and attempts to construct intelligent interfaces for applications are underway.

sp-Carbon Incorporated Conductive Metal-Organic Framework as Photocathode for Photoelectrochemical Hydrogen Generation.

Metal-organic frameworks (MOFs) have attracted increasing interest for broad applications in catalysis and gas separation due to their high porosity. However, the insulating feature and the limited active sites hindered MOFs as photocathode active materials for application in photoelectrocatalytic hydrogen generation. Herein, we develop a layered conductive two-dimensional conjugated MOF (2D c-MOF) comprising sp-carbon active sites based on arylene-ethynylene macrocycle ligand via CuO4 linking, named as Cu3 HHAE2 . This sp-carbon 2D c-MOF displays apparent semiconducting behavior and broad light absorption till the near-infrared band (1600 nm). Due to the abundant acetylene units, the Cu3 HHAE2 could act as the first case of MOF photocathode for photoelectrochemical (PEC) hydrogen generation and presents a record hydrogen-evolution photocurrent density of ≈260 µA cm-2 at 0 V vs. reversible hydrogen electrode among the structurally-defined cocatalyst-free organic photocathodes.

Spatial Confinement Tunes Cleavage and Re-Formation of C=N Bonds in Fluorescent Molecules.

Molecules in confined spaces exhibit unusual behaviors that are not typically observed in bulk systems. Such behavior can provide alternative strategies for exploring new reaction pathways. Cleavage of the C=N bond of Nile red (NR) in solution is an irreversible reaction. Here, we used spatial confinement within a cationic micelle-confined system to convert this reaction to a reversible process. The fluorescence of NR shifted between red and green for nine cycles. The new chemical pathway based on spatial confinement can be attributed to two factors: increasing the local concentration of reactants and reducing the reaction energy barrier. This effect is supported by both experimental evidence and theoretical calculations. The cross-linked silica shell comprising the confinement chamber stabilizes the enclosed molecules. This reduces fluorophore leakage and maintains fluorescence intensity in most environments, including in solution, on paper, and in hydrogel films, and expands practical applications in encrypted information and multi-informational displays.

Deformable Metal-Organic Framework Nanosheets for Heterogeneous Catalytic Reactions.

The dynamic status near the surface of a catalyst can significantly affect the catalytic process, because the overall reaction rate depends on the mass velocity of product attachment and reactant detachment. As a dominant diffusion mechanism, molecular diffusion is known as a slow process that inhibits the fast contact between the reactants and the heterogeneous catalyst, which depresses catalytic conversion efficiency. Herein, we report a strategy that can break such a stagnant layer to facilitate the mass transport toward the catalyst surface, wherein Pd nanocubes (NCs) encapsulated in soft metal-organic framework (MOF) nanosheets are used as catalysts for the hydrogenation reactions. The soft MOF supports render deformable features to enhance mass transport across the Pd NCs, which is vital to enhance the catalyst performance. In combination with numerical simulations, we identify the deformable MOF driven by the shear force of flowing fluid to increase dye adsorption and catalytic conversion by 5- and 3-fold, respectively, as compared to a counterpart system containing nondeformable MOFs. The catalytic efficiency presents a volcano-type trend with the length-to-spacing ratio of MOF nanosheet being designed and reaches the maximum with a length-to-spacing ratio of 2:1. This technique provides unique opportunities to design a proof-of-concept self-propelled catalysis on the basis of a greater mechanistic understanding of heterogeneous catalytic reactions.

General Strategy to Optimize Gas Evolution Reaction via Assembled Striped-Pattern Superlattices.

Redesigning heterogeneous catalysts so that they can simultaneously integrate the efficiency and durability under reaction environments with respect to gas fuel production, such as hydrogen (H2), oxygen (O2), or carbon monoxide (CO), has proven challenging. In this work, we report the successful template-assisted printing-based assembly of platinum (Pt) nanoparticles (NPs) into striped-pattern (SP) superlattices to produce H2. In comparison to drop-casting flat Pt NPs films, SP superlattices lead to higher mass transference and smaller bubble stretch force, representing a general strategy to improve the efficiency and durability of pre-existed Pt catalysts for the hydrogen evolution reaction (HER), as well as higher current densities than commercial Pt/C, Pt NP films, and many of the other Pt-based or non-Pt-based HER catalysts reported in the literature. The generic nature of template-assisted printing leads to flexibility in the composition, size, and shape of the constituent NPs or molecules, and thus extends such an accelerated technique for producing the oxygen evolution reaction and electrochemical reduction of CO2 to CO.

Understanding the Role of Metal-Organic Frameworks in Surface-Enhanced Raman Scattering Application.

Metal-organic frameworks (MOFs), built from organic linkers and metal ions/clusters, have emerged as highly promising materials for wide applications. Combining highly porous crystalline MOFs with the surface-enhanced Raman scattering (SERS) technique can achieve unprecedented advantages of high selectivity, high sensitivity, and expedience in analysis and detection. In this critical review, the aim is to present a comprehensive review of recent advances in understanding of the roles of MOFs in MOF-SERS systems, particularly their structure-to-property correlation. Key examples are selected from representative literature to illustrate critical concepts and the MOF-based property-dependent applications are particularly emphasized. Finally, the barriers, future trends, and prospects for further advances in MOF-SERS platforms are also discussed.

A fish scale-like magnetic nanomaterial as a highly efficient sorbent for monitoring the changes in auxin levels under cadmium stress.

Sorbents with high surface utilization and good dispersibility are of great importance for the extraction performance of magnetic solid-phase extraction (MSPE). In this study, a fish scale-like magnetic nanomaterial (Co@Co3O4/OCN) was synthesized, which can be used as a highly efficient MSPE sorbent due to its strong magnetism, special morphology, doping of N element, numerous micro-mesopore cavities and organic functional groups (hydroxyl and carboxyl). Furthermore, a Co@Co3O4/OCN-based MSPE method for monitoring the changes in the levels of three auxins (indole-3-acetic acid, indole-3-propionic acid and 3-indole butyric acid) was successfully established. Wide linear ranges (1.0-1000.0 pg mL-1) with good correlation coefficients (R > 0.9992), low limits of detection (LODs, 0.2-4.0 pg mL-1) and satisfactory repeatability (RSD ≤5.9%, n = 3) were obtained. Using the developed method, various growth parts and different growth periods of plants under Cd stress were monitored. The results showed that auxins in various parts of plants showed differential response under Cd stress, and there was a threshold for the changes in auxin levels against Cd stress. This indicates that the developed fish scale-like Co@Co3O4/OCN nanomaterial has a good application prospect for enriching small molecular targets containing hydroxyl and carboxyl groups.

Universal Strategy for Improving the Sensitivity of Detecting Volatile Organic Compounds by Patterned Arrays.

The diffusion of target analytes is a determining factor for the sensitivity of a given gas sensor. Surface adsorption results in a low-concentration region near the sensor surface, producing a concentration gradient perpendicular to the surface, and drives a net flux of molecules toward solid reactive reagents on the sensor surface, that is, vertical diffusion. Here, organic semiconductor supramolecules were patterned into micromeshed arrays to integrate vertical and horizontal diffusion pathways. When used as a gas sensor, these arrays have an order of magnitude higher sensitivity than traditional film-based sensors. The sensor sensitivity ramp down with the increase in coverage density of reactive reagents, yielding two linear regions demarcated by 0.3 coverage, which are identified by the experimental results and simulations. The universal nature of template-assisted patterning allows adjustments in the composition, size, and shape of the constituent material, including nanofibers, nanoparticles, and molecules, and thus serves to improve the sensitivity of gas sensors for detecting various volatile organic compounds.

Effective Extraction of Domoic Acid from Seafood Based on Postsynthetic-Modified Magnetic Zeolite Imidazolate Framework-8 Particles.

Domoic acid (DA) is a naturally occurring neurotoxin known to bioaccumulate in marine products. Despite its hypertoxicity, the enrichment and analysis of trace DA in complex marine organisms remains a challenge. We describe herein the fabrication of a postsynthetic-modified magnetic zeolite imidazolate framework-8 (Fe3O4 SPs@ZIF-8/Zn2+), based on Fe3O4 superparticles, for the adsorption of DA from complex biological matrices. The adsorption of DA is rapid (∼5 min) and occurs through strong electrostatic interactions and chelation with coordinatively unsaturated zinc sites on the surface of Fe3O4 SPs@ZIF-8/Zn2+. Employing our Fe3O4 SPs@ZIF-8/Zn2+ sorbent in a magnetic solid-phase extraction, followed by liquid chromatographic separation and tandem mass spectrometric detection, resulted in a facile, rapid, efficient, and sensitive method for the enrichment and detection of trace DA in marine products. After optimization, this method yielded satisfactory precision (relative standard deviation ≤3.4%; n = 5) with a high degree of linearity from 1.0 to 1000.0 pg mL-1 ( r2 = 0.9997) and a detection limit of 0.2 pg mL-1 (S/N = 3). Recoveries of 93.1-102.3% were obtained in spiked aquatic products. In addition, trace levels of DA (49.2 pg mL-1) were found in shellfish samples, confirming the applicability of our Fe3O4 SPs@ZIF-8/Zn2+ adsorbent for the detection of DA in seafood.

Detection of Exhaled Volatile Organic Compounds Improved by Hollow Nanocages of Layered Double Hydroxide on Ag Nanowires.

To detect biomarkers from human exhalation, air flow dynamics on the nanoparticle surface were explored by a surface-enhanced Raman scattering (SERS) sensor. A hollow Co-Ni layered double hydroxide (LDH) nanocage on Ag nanowires (Ag@LDH) was prepared. Ag nanowires provided amplified Raman signals for trace determination; hollow LDH nanocages served as the gaseous confinement cavity to improve capture and adsorption of gaseous analytes. The Raman intensity and logarithmic analyte concentration exhibit an approximately linear relationship; the detection limit of SERS sensors for aldehyde is 1.9×10-9 v/v (1.9 ppb). Various aldehydes in mixed mimetic gas are distinguished by Raman spectra statistical analysis assisted by multivariate methods, including principal component analysis and hierarchical cluster analysis. The information was recorded in a barcode, which can be used for the design and development of a desktop SERS sensor analysis system for large-scale lung cancer detection.

A Metastable Crystalline Phase in Two-Dimensional Metallic Oxide Nanoplates.

A simple method was adopted in which ultrathin cerium oxide nanoplates (<1.4 nm) were synthesized to increase the surface atomic content, allowing transformation from a face-centered cubic (fcc) phase to a body-centered tetragonal (bct) phase. Three types of cerium oxide nanoparticles of different thicknesses (1.2 nm ultrathin nanoplates, 2.2 nm nanoplates, and 5.4 nm nanocubes) were examined using transmission electron microscopy and X-ray diffraction. The metastable bct phase was observed only in ultrathin nanoplates. Thermodynamic energy analysis confirmed that the surface energy of the ultrathin nanoplates is the cause of the remarkable stabilization of the metastable bct phase. The mechanism of surface energy regulation can be expanded to other metallic oxides, thus providing a new means for manipulating and stabilizing novel materials under ambient conditions that otherwise would not be recovered.

Understanding the Selective Detection of Fe3+ Based on Graphene Quantum Dots as Fluorescent Probes: The Ksp of a Metal Hydroxide-Assisted Mechanism.

Graphene quantum dots (GQDs) have been widely used as fluorescence probes to detect metal ions with satisfactory selectivity. However, the diverse chemical structures of GQDs lead to selectivity for multiple metal ions, and this can lead to trouble in the interpretation of selectivity due to the lack of an in depth and systematic analysis. Herein, bare GQDs were synthesized by oxidizing carbon black with nitric acid and used as fluorescent probes to detect metal ions. We found that the specific ability of GQDs to recognize ferric ions relates to the acidity of the medium. Specifically, we demonstrated that the coordination between GQDs and Fe3+ is regulated by the pH of the aqueous GQDs solution. Dissociative Fe3+ can coordinate with the hydroxyl groups on the surface of the GQDs to form aggregates (such as iron hydroxide), which induces fluorescence quenching. A satisfactory selectivity for Fe3+ ions was achieved under relatively acidic conditions; this is because of the extremely small Ksp of ferric hydroxide compared to those of other common metal hydroxides. To directly survey the key parameter for Fe3+ ion specificity, we performed the detection experiment in an environment free of interference from the buffer solution, noninherent groups, and other complex factors. This study will help researchers understand the selectivity mechanisms of GQDs as fluorescence probes for metal ions, which could guide the design of other GQD-based sensor platforms.

Investigation of contact characteristics and frictional properties of natural articular cartilage at two different surface configurations.

Natural cartilage surfaces were macroscopically curved with multi-porous viscoelastic biologic materials with extremely high water, but whether curved surface configuration could play an important role on the contact and frictional properties of natural cartilages fails to be completely understood up to now. In this current study, cartilage samples came from the 18-24 month-old bovine femora. Contact characteristic and frictional properties at two cartilage configurations were investigated using the UMT-2 testing rig and the five-point sliding average method would be adopted to analyze these tested data. These results indicated the surface displacement was extremely associated with the plate cartilage surface and seemed to be a representative of cartilage surface configuration. The summit of the surface load lagged behind that of the surface displacement at the same condition. Coefficient of friction showed obviously different variation with time at two cartilage surface configurations due to the fact that these two surface displacements had different amplitudes and opposite directions as a function of the sliding length. Therefore, surface configuration played the main role on these variables of contact displacement, contact load and coefficient of friction due to the direction and magnitude of the surface displacement while applied load and sliding velocity had a secondary role. Natural cartilage surfaces were macroscopically curved with multi-porous viscoelastic biologic materials with extremely high water, but whether curved surface configuration could play an important role on the contact and frictional properties of natural cartilages fails to be completely understood up to now. In this study, two different cartilage configurations were adopted to investigate natural cartilage properties, and the five-point sliding average method would be used to analyze these tested data. These results indicated the contact displacement was consisted of cartilage deformation and surface displacement while contact load was composed of steady load and surface load (as shown in the figure, panels (a) and (b)). Surface displacement was greatly associated with the plate cartilage surface and seemed to be a representative of cartilage surface configuration. These two surface displacements had different amplitudes and opposite directions as a function of the sliding length (as shown in panel (c)). The summit of the surface load lagged behind that of the surface displacement at the same condition (as shown in panel (d)). Surface displacement and surface load in the contact characteristic of natural cartilages were extremely related with the cartilage configurations. and their correlation coefficients varied periodically with the moving time (as shown in panel (e)). Coefficient of friction showed obviously different variation with time (as shown in panel (f)). Therefore, surface configuration played the main role on these variables of contact displacement, contact load and coefficient of friction due to the direction and magnitude of the surface displacement while applied load and sliding velocity had a secondary role. Variation in contact and frictional properties of natural cartilage at two different surface configurations (a) Contact displacement and its parts varied with time; (b) Contact load and its parts varied with time;

Multi-metallic MOF based composites for environmental applications: synergizing metal centers and interactions.

The escalating threat of environmental issues to both nature and humanity over the past two decades underscores the urgency of addressing environmental pollutants. Metal-organic frameworks (MOFs) have emerged as highly promising materials for tackling these challenges. Since their rise in popularity, extensive research has been conducted on MOFs, spanning from design and synthesis to a wide array of applications, such as environmental remediation, gas storage and separation, catalysis, sensors, biomedical and drug delivery systems, energy storage and conversion, and optoelectronic devices, etc. MOFs possess a multitude of advantageous properties such as large specific surface area, tunable porosity, diverse pore structures, multi-channel design, and molecular sieve capabilities, etc., making them particularly attractive for environmental applications. MOF-based composites inherit the excellent properties of MOFs and also exhibit unique physicochemical properties and structures. The tailoring of central coordinated metal ions in MOFs is critical for their adaptability in environmental applications. Although many reviews on monometallic, bimetallic, and polymetallic MOFs have been published, few reviews focusing on MOF-based composites with monometallic, bimetallic, and multi-metallic centers in the context of environmental pollutant treatment have been reported. This review addresses this gap by providing an in-depth overview of the recent progress in MOF-based composites, emphasizing their applications in hazardous gas sensing, electromagnetic wave absorption (EMWA), and pollutant degradation in both aqueous and atmospheric environments and highlighting the importance of the number and type of metal centers present. Additionally, the various categories of MOFs are summarized. MOF-based composites demonstrate significant promise in addressing environmental challenges, and this review provides a clear and valuable perspective on their potential in environmental applications.

Effect of synthesis temperature on the structural morphology of a metal-organic framework and the capacitor performance of derived cobalt-nickel layered double hydroxides.

Three-dimensional interconnected nickel-cobalt layered double hydroxides (NiCo-LDHs) were prepared on nickel foam by ion exchange using a cobalt-based metal-organic framework (Co-MOF) as a template at different temperatures. The effects of the Co-MOF preparation temperature on the growth, mass, morphology, and electrochemical properties of the Co-MOF and derived NiCo-LDH samples were studied. The synthesis temperature from 30 to 50 °C gradually increased the mass of the active material and the thickness of the Co-MOF sheets grown on the nickel foam. The higher the temperature is, the larger the proportion of Co3+. ß-Cobalt hydroxide (ß-Co(OH)2) sheets were generated above 60 °C. The morphology and mass loading pattern of the derived flocculent layer clusters of NiCo-LDH were inherited from metal-organic frameworks (MOFs). The areal capacitance of NiCo-LDH shows an inverted U-shaped curve trend with increasing temperature. The electrode material synthesized at 50 °C had a tremendous specific capacitance of 7631 mF·cm-2 at a current density of 2 mA·cm-2. The asymmetric supercapacitor assembled with the sample and active carbon (AC) achieved an energy density of 55.0 Wh·kg-1 at a power density of 800.0 W·kg-1, demonstrating the great potential of the NiCo-LDH material for energy storage. This work presents a new strategy for designing and fabricating advanced green supercapacitor materials with large power and energy densities.