Design Of Metal-organic Frameworks Research Articles

A general flame aerosol route to kinetically stabilized metal-organic frameworks

Metal-organic frameworks (MOFs) are highly attractive porous materials with applications spanning the fields of chemistry, physics, biology, and engineering. Their exceptional porosity and structural flexibility have led to widespread use in catalysis, separation, biomedicine, and electrochemistry. Currently, most MOFs are synthesized under equilibrium liquid-phase reaction conditions. Here we show a general and versatile non-equilibrium flame aerosol synthesis of MOFs, in which rapid kinetics of MOF formation yields two distinct classes of MOFs, nano-crystalline MOFs and amorphous MOFs. A key advantage of this far-from-equilibrium synthesis is integration of different metal cations within a single MOF phase, even when this is thermodynamically unfavorable. This can, for example, produce single-atom catalysts and bimetallic MOFs of arbitrary metal pairs. Moreover, we demonstrate that dopant metals (e.g., Pt, Pd) can be exsolved from the MOF framework by reduction, forming nanoclusters anchored on the MOF. A prototypical example of such a material exhibited outstanding performance as a CO oxidation catalyst. This general synthesis route opens new opportunities in MOF design and applications across diverse fields and is inherently scalable for continuous production at industrial scales.

Achievements and Challenges in Surfactants-Assisted Synthesis of MOFs-Derived Transition Metal-Nitrogen-Carbon as a Highly Efficient Electrocatalyst for ORR, OER, and HER.

Metal-organic frameworks (MOFs) are excellent precursors for preparing transition metal and nitrogen co-doped carbon catalysts, which have been widely utilized in the field of electrocatalysis since their initial development. However, the original MOFs derived catalysts have been greatly limited in their development and application due to their disadvantages such as metal atom aggregation, structural collapse, and narrow pore channels. Recently, surfactants-assisted MOFs derived catalysts have attracted much attention from researchers due to their advantages such as hierarchical porous structure, increased specific surface area, and many exposed active sites. This review mainly focuses on the synthesis methods of surfactants-assisted MOFs derived catalysts and comprehensively introduces the action of surfactants in MOFs derived materials and the structure-activity relationship between the catalysts and the oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction performance. Apparently, the aims of this review not only introduce the status of surfactants-assisted MOFs derived catalysts in the field of electrocatalysis but also contribute to the rational design and synthesis of MOFs derived catalysts for fuel cells, metal-air cells, and electrolysis of water toward hydrogen production.

MOF-on-MOF Growth: Inducing Naturally Nonpreferred MOFs and Atypical MOF Growth.

ConspectusOverflowing metal-organic frameworks (MOFs) have been synthesized from a wide range of metal and organic components for specific purposes and intellectual curiosity. Each MOF has unique chemical and structural characteristics directed by the incorporated components, metal ions (or clusters), organic linkers, and their intrinsic coordination interactions. These incorporated components and structural characteristics are two pivotal factors influencing MOFs' fundamental properties and subsequent applications. Therefore, selecting the appropriate metal and organic components, considering their innate chemical and structural properties, is crucial to endow the final MOFs with the desired properties. Ultimately, producing MOFs with a desired structure using ideal components is the best approach to achieving the best MOFs tailored for specific purposes with desired properties. However, achieving MOFs with the intended structure from chosen components remains underdeveloped. In many cases, the resulting MOF structure is governed by the thermodynamically and/or kinetically preferred configuration (refers to a naturally preferred structure) of the chosen components and given reaction conditions. Additionally, producing hybrid MOFs with complex components, structures, and morphologies presents a great opportunity to obtain special MOFs with advanced properties and functions. In this Account, we outline our group's efforts over the past few years to develop naturally nonpreferred MOFs through the induced MOF-on-MOF growth process and atypical hybrid MOFs via nonstandard MOF-on-MOF growth. First, we highlight the prime strategy for producing naturally nonpreferred MOFs based on template-induced MOF-on-MOF growth. In this section, we discuss the two basic growth behaviors, isotropic and anisotropic growth of naturally nonpreferred MOFs, determined by the degree of matching between the cell lattices of the two MOFs. Second, we introduce the MOF farming concept for the productive cultivation and effective harvesting of naturally nonpreferred MOFs made by MOF-on-MOF growth. Here we discuss the importance of selecting the ideal MOF template for productive growth and developing an efficient method for harvesting cultivated MOFs. Next, we describe atypical anisotropic MOF-on-MOF growths between two MOFs with mismatched cell lattices. In this section, we introduce tip-to-middle MOF-on-MOF growth involving self-structural adjustment of the secondary MOF, logical inference of unidentified MOF structures based on MOF-on-MOF growth behavior and morphological features, and MOF-on-MOF growth accompanied by etching and transformation of the template. Finally, we discuss the perspectives and challenges of MOF-on-MOF growth and the synthesis of naturally nonpreferred MOFs. We hope that this Account offers valuable insights into the rational design and development of MOFs with desired structural and compositional characteristics, leading to the creation of ideal MOFs.

Metal-Organic Frameworks for Sustainable Crop Disease Management: Current Applications, Mechanistic Insights, and Future Challenges.

Efficient management of crop diseases and yield enhancement are essential for addressing the increasing food demands due to global population growth. Metal-organic frameworks (MOFs), which have rapidly evolved throughout the 21st century, are notable for their vast surface area, porosity, and adaptability, establishing them as highly effective vehicles for controlled drug delivery. This review methodically categorizes common MOFs employed in crop disease management and details their effectiveness against various pathogens. Additionally, by critically evaluating existing research, it outlines strategic approaches for the design of drug-delivery MOFs and explains the mechanisms through which MOFs enhance disease resistance. Finally, this paper identifies the current challenges in MOF research for crop disease management and suggests directions for future research. Through this in-depth review, the paper seeks to enrich the understanding of MOFs applications in crop disease management and offers valuable insights for researchers and practitioners.

Ammonia Storage in Metal-Organic Framework Materials: Recent Developments in Design and Characterization.

Since the advent of the Haber-Bosch process in 1910, the global demand for ammonia (NH3) has surged, driven by its applications in agriculture, pharmaceuticals, and energy. Current methods of NH3 storage, including high-pressure storage and transportation, present significant challenges due to their corrosive and toxic nature. Consequently, research has turned towards metal-organic framework (MOF) materials as potential candidates for NH3 storage due to their potential high adsorption capacities and structural tunability. MOFs are coordination networks composed of metal nodes and organic linkers, offering unprecedented porosity and surface area, and allowing incorporation of various functional groups and metal sites that can enhance NH3 adsorption. However, the stability of MOFs in the presence of NH3 is a significant concern since many degrade upon exposure to NH3, primarily due to ligand displacement and framework collapse. To address this, recent studies have focused on the synthesis and postsynthetic modification of MOFs to enhance both NH3 uptake and stability. In this Account, we summarize recent developments in the design and characterization of MOFs for NH3 storage. The choice of metal centers in MOFs is crucial for stability and performance. High-valence metals such as AlIII and TiIV form strong metal-linker bonds, enhancing the stability of the framework to NH3. The MFM-300 series of materials composed of high-valence 3+ and 4+ metal ions and carboxylic linkers demonstrates high stability and high NH3 uptake capacities. Ligand functionalization is another effective strategy for improving the NH3 adsorption. Polar functional groups such as -NH2, -OH, and -COOH enhance the interaction between the framework and NH3, particularly at low partial pressures, while postsynthetic modification allows fine-tuning of these functionalities to optimize the framework for higher adsorption capacities and stability. For example, MFM-303(Al), incorporating free carboxylic acid groups, exhibits a high NH3 packing density comparable to that of solid NH3. Creating defect sites by removing linkers or adding metal ions increases the number of active sites available for NH3 adsorption and shows promise for enhancing uptake. UiO-66, a stable MOF framework, can be modified to include defect sites, significantly enhancing the level of NH3 uptake. The full characterization of MOFs and especially their interactions with NH3 are vital for understanding and improving their performance. Techniques such as neutron powder diffraction (NPD), inelastic neutron scattering (INS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), electron paramagnetic resonance (EPR) spectroscopy, and solid-state nuclear magnetic resonance (ssNMR) spectroscopy can elucidate host-guest interactions and binding dynamics between NH3 and the framework structure and afford crucial information for the future design and rational development of new sorbents. This Account highlights our current strategies for the synthesis and characterization of MOFs for NH3 capture, providing an overview of this rapidly evolving field.

MOFs with the Stability for Practical Gas Adsorption Applications Require New Design Rules.

Metal-organic frameworks (MOFs) have been widely studied for their ability to capture and store greenhouse gases. However, most computational discovery efforts study hypothetical MOFs without consideration of their stability, limiting the practical application of novel materials. We overcome this limitation by screening hypothetical ultrastable MOFs that have predicted high thermal and activation stability, as judged by machine learning (ML) models trained on experimental measures of stability. We enhance this set by computing the bulk modulus as a measure of mechanical stability and filter 1102 mechanically robust hypothetical MOFs from a database of ultrastable MOFs (USMOF DB). Grand Canonical Monte Carlo simulations are then employed to predict the gas adsorption properties of these hypothetical MOFs, alongside a database of experimental MOFs. We identify privileged building blocks that lead MOFs in USMOF DB to show exceptional working capacities compared to the experimental MOFs. We interpret these differences by training ML models on CO2 and CH4 adsorption in these databases, showing how poor model transferability between data sets indicates that novel design rules can be derived from USMOF DB that would not have been gathered through assessment of structurally characterized MOFs. We identify geometric features and node chemistry that will enable the rational design of MOFs with enhanced gas adsorption properties in synthetically realizable MOFs.

Biomimetic Channels Design in Metal-Organic Framework Enabling Highly Lithium-Ion Conduction for Lithium-Metal Batteries.

Solid-state electrolytes (SSEs) based on metal-organic frameworks (MOFs) are an ideal material for constructing high-performance lithium metal batteries (LMBs). However, the low ion conductivity and poor interface contact (especially at low temperatures) still seriously hinder its further application. Herein, inspired by the Na+/K+ conduction in biology systems, a series (NH2, OH, NH-(CH2)3-SO3H)-modified MIL-53-X as SSEs is reported. These functional groups are similar to anions suspended in biological ion channels, partially repelling anions while allowing cations to be effectively transported through pore channels. Subsequently, MIL-53-X with hierarchical pore structure (H-MIL-53-X) is obtained by introducing lauric acid as a regulator, and then the effects of structural design and morphology control on its performance are explored. The conductivity of H-MIL-53-NH-SO3Li with multi-level pore structure and modified by sulfonic acid groups reached 2.2×10-3Scm-1 at 25°C, lithium-ion transference number of 0.78. Besides, the H-MIL-53-NH-SO3Li still has an excellent conductivity of 10-4Scm-1 at -40°C. Additionally, LiFePO4/Li batteries equipped with H-MIL-53-NH-SO3Li SSEs could operate stably for over 200 cycles at 0.1C. The strategy of combining structural and morphological design of MOFs with biomimetic ion channels opens new avenues for the design of high-performance SSEs.

High-capacity and long-life Fe2O3/MOFs composite anodes: Preparation, characterization, morphology regulation and electrochemical performance

Among the various transition metal oxides used in lithium-ion battery anodes, iron oxide (Fe2O3) has received extensive attention due to its low cost, good environmental compatibility and high theoretical capacity. However, the volume expansion and structural collapse during the charging-discharging cycling process significantly limited the practical application of Fe2O3. Herein, we demonstrate enhanced electrochemical properties and stability of Fe2O3 by anchoring it on metal-organic frameworks (MOFs). Through adjusting the MOF ligands and introducing humic acid (HA), we reached rational control of the morphology for the Fe2O3/MOF composites. The optimized sample, namely Fe2O3@HA-Fe-ATA, shows 3D cauliflower-like structure with abundant pores, which are beneficial to the active sites exposure, electrolyte penetration, as well as the tolerance toward volume expansion. Consequently, high reversible capacity of 1442.7 mAh g−1 (at 0.1 A g−1), excellent rate performance (<11 % capacity decrease when current density increases from 0.1 A g−1 to 1 A g−1), and satisfactory cycle stability (91 % capacity retention after 500 cycles at 1 A g−1) are obtained. This work demonstrates that the rational design of MOF by introduction of appropriate ligand is a very efficient approach to optimize the electrochemical properties of the resultant electrode material.

Metal–Organic Frameworks as a Catalyst and Catalyst Support in Fuel Cells: From Challenges to Catalytic Application

AbstractThe innovation of high‐performance, stable electrocatalysts for clean energy systems faces significant challenges. Metal‐organic frameworks (MOFs), with their porous nature, flexible structures, and homogeneous active site dispersion, have gained interest as unique precursors for carbon‐based catalysts. MOFs' properties significantly enhance catalytic performance in fuel cells. This review highlights recent advancements in MOF design for oxygen electrocatalysis in fuel cells, while also discussing perspectives for future material innovations to improve catalytic activity in this emerging field.

Rapidly tailor metal–organic frameworks for arsenate removal using graph convolutional neural networks

Metal-organic frameworks (MOFs) are effective materials for the removal of highly toxic arsenates (As(V)). However, the intricate structure–activity relationships of MOFs for As(V) removal remain unclear, thus impeding its targeted fabrication. In this work, we used the graph convolutional neural network to integrate MOFs’ chemical composition, physical structure, and adsorption environment, thereby developing an end-to-end predictive model for As(V) adsorption by MOFs. The model’s high coefficient of determination, low mean absolute error, and experimental verification of MOFs synthesized based on model predictions not previously used in the As (V) adsorption confirmed the precision and general applicability of the model. Our constructed model identified two key features for adsorption, i.e., metal nodes and pore features, and the modular blocks for constructing MOFs. The strategic design for MOFs to absorb As(V) informed by the model, emphasized integrating open single or binuclear metal nets with aromatic di- or tricarboxylic acid linkers within a robust three-dimensional topological net. This work highlights the integration of predictive modeling and structural refinement to enhance MOF design for As (V) adsorption, even in more other pollutants.

Ethylene Dimerization, Isomerization and Trimerization: Mechanistic Insights into Competing Pathways on Metal–Organic Framework Supported Metal Hydrides

AbstractCatalytic ethylene oligomerization is important in the petrochemical industry, as it produces valuable products like linear alpha‐olefins (LAOs) for the synthesis of polymers and specialty chemicals. Catalysts, typically transition metal complexes or metal‐containing materials, play a crucial role in selective oligomerization by providing active sites for ethylene activation and controlling product distribution. Recently, defective metal‐organic frameworks (MOFs) with well‐defined structures and unsaturated active sites have emerged as potential catalysts for ethylene oligomerization. In this study, we employ density functional theory calculations to investigate the energetic selectivity of competing pathways (including dimerization, isomerization and trimerization) during ethylene oligomerization on defective HKUST‐1 supported metal hydrides (H−M–DHKUST‐1, M: Co, Ni, Ru, Rh and Pd). On all the five hydrides, ethylene dimerization is found to be more preferential than trimerization and isomerization. In the microenvironment of defective paddlewheel of HKUST‐1, isomerization is highly unfavorable compared with dimerization because of high energy required for chain walk, and 1‐butene is expected to be the major product on all the five hydrides. Analysis of NBO charges reveals a notable reduction in cationic nature at the metal site on H−Ru–DHKUST‐1, which facilitates β‐hydride elimination for dimerization. The microscopic insights from this computational study might facilitate the rational design of new MOFs and other MOF‐supported catalysts for selective ethylene oligomerization.

Enhancing arsenate removal through interpretable machine learning guiding the modular design of metal–organic frameworks

The modular design of metal–organic frameworks (MOFs) for enhancing arsenate (As(V)) adsorption remains a challenge. We have developed twelve interpretable machine learning prediction models by integrating six decision tree-based algorithms with two molecular fingerprints, Morgan and MACCS. The optimal XGBoost-Morgan model, with its high determination coefficient of 0.97 and low root mean square error of 11.78, not only demonstrates excellent prediction and generalization capabilities in As(V) adsorption capacity, but also validates the feasibility of modeling concepts by feature engineering adopted in this work. Our comprehensive model interpretation initiates with the molecular fragment composition of the organic linkers, the secondary building units, and the topological nets, that constitute MOFs, and structure parameters. It culminates in the proposal of a reticular chemistry design scheme specifically tailored for the adsorption of As(V) by MOFs. Furthermore, it delineates the optimal environmental conditions conducive to effective As(V) adsorption. We anticipate that our MOF design strategy will be extensively applicable to the target removal of pollutants.

Constructing Isoreticular Metal-Organic Frameworks by Silver-Carbon Bonds.

The incorporation of new coordinate bonds and the development of universal methods for new structures have always been of major interest in metal-organic framework (MOF) research. The poor reversibility makes metal-carbon (M-C) bonds a great challenge to adopt as linkages to construct crystalline MOFs. Herein, three isoreticular microcrystalline MOFs connected by silver-carbon (Ag-C) bonds are presented for the first time and named AgC-MOFs. Their structures contain a double coordination mode (σ and π) between Ag(I) and alkynyl. The three AgC-MOFs all exhibit three-dimensional (3D) frameworks with uniform one-dimensional (1D) hexagonal channels, and the pore width could be tuned from 1.1 to 1.8 nm. The construction of crystalline MOFs using poorly reversible Ag-C coordinate bonds extends the nexuses for the MOF structure and lights up more possibilities for the systematic design of MOFs.

Enhanced Fenton catalytic degradation of methylene blue by the synergistic effect of Fe and Ce in chitosan-supported mixed-metal MOFs (Fe/Ce-BDC@CS)

Methylene blue (MB) is a refractory organic pollutant that poses a potential threat to the aquatic environment. Fenton reaction is considered a primrose strategy to treat MB. However, the traditional Fenton process is plagued by narrow pH application range, poor stability, and secondary pollution. To solve these problems, many Fenton-like catalysts including metal-organic frameworks (MOFs) have been prepared. Herein, a novel bimetallic MOF (Fe/Ce-BDC@CS) was prepared through simple adsorption for the effective removal of MB, where chitosan (CS) was used as the carrier. The degradation performance of Fe/Ce-BDC@CS (100 % within 20 min) was better than that of most reported monometallic MOFs. Moreover, Fe/Ce-BDC@CS exhibited good repeatability and its anti-interference performance of some inorganic ions was also remarkable. Column loading experiments showed that the removal efficiency of MB was still about 50 % over 155 h with a flowing speed of 0.30 L/h. Comparative analysis indicated that such excellent performances could be attributed to the synergistic effect between Fe and Ce. Furthermore, the results of quenching tests indicate that OH, O2−, and 1O2 contributed to MB degradation. In brief, Fe/Ce-BDC@CS has promising prospects in MB treatment, which can provide scientific references for the design and application of bimetallic MOFs.

Flexible Metal-Organic Frameworks: From Local Structural Design to Functional Realization.

ConspectusFlexible metal-organic frameworks (MOFs), also known as soft porous crystals, exhibit dynamic behaviors in response to external physical and chemical stimuli such as light, heat, electric or magnetic field, or the presence of particular matters, on the premise of maintaining their crystalline state. The reversible structural transformation of flexible MOFs, a unique characteristic seldomly found in other types of known solid-state materials, affords them distinct properties in the realms of molecule separation, optoelectronic devices, chemical sensing, information storage, biomedicine applications, and so on. The mechanisms underlying their dynamic behaviors can be comprehensively investigated at the molecular level by means of in situ single-crystal or powder X-ray diffraction as well as other in situ spectroscopic techniques due to the high regularity of these crystalline materials during stimuli-responsive phase transitions. Through the introduction of specific stimuli-responsive groups/moieties into the well-defined and ordered molecular arrays, targeted applications can be achieved, and the performance of flexible MOFs can also be further improved via rational structural design.In this Account, we summarize our progress on the design, synthesis, and applications of flexible MOFs over the past few years. First, we highlight the construction principle of flexible MOFs, emphasizing the pivotal role of local structural design. Using an F-modified ligand, a flexible MOF with remarkable structural transformations can be obtained; the regulation of the metal coordination environment and interpenetrating frameworks is also crucial for achieving flexible MOFs. We also propose a strong correlation strategy based on the supramolecular interactions between the guest molecules and the framework, which realizes the temperature-responsive dynamic spatial "open-closed" regulation. Mechanisms of the dynamic behaviors investigated by the in situ techniques were also presented for the obtained materials. Second, some representative specific applications of the newly developed dynamic coordination systems were reviewed. The gas molecule responsive flexible MOFs show efficient short-chain alkane separation properties with discriminatory sorption behavior toward similar gaseous substrates. Smart sensing of temperature, pressure, and volatile organic compounds was achieved by several novel flexible fluorescent MOFs, with optimization potential through state-of-the-art chemical design. Furthermore, multiferroic materials with multiple bistable states and high working temperatures were also obtained based on flexible MOFs.Finally, we provide a discussion of the challenges of flexible MOFs in future research, including precise and efficient synthesis, in-depth structure-property relationship investigation, performance optimization, and industrialization. We hope that this Account will stimulate further research interest in developing next-generation smart materials based on flexible MOFs for applications in challenging chemical separation, extreme environmental sensing, massive information storage, and beyond.

Electrostatic assembly of metal organic frameworks nanocubes on electrochemically exfoliated graphene nanoflakes: Superior role in flame retardance

The extensive usage of epoxy resin (EP) is facing the head-scratching challenge of high fire hazard. As such, the electrostatic assembly of metal organic frameworks (MOFs) nanocubes on electrochemically exfoliated graphene nanoflakes is performed to acquire the hybrid of PG@UIO. The corresponding role and behavior in flame retardance are explored in detail. By adding 2.0 wt% PG@UIO, the reductions in peak heat release rate, total heat release, peak smoke production rate, peak CO yield, peak CO2 yield reach 49.2 %, 44.3 %, 56.1 %, 57.7 % and 51.3 %. The in-situ volatiles analysis points out the reductions of 35.1 %, 29.4 %, 50.8 %, 32.5 % in the maximal intensities of aromatic compounds, ethers, CO and HCN. The mechanical interlocking area between PG@UIO nanostructures and EP molecular chains contributes to the enhanced mechanical performances. Specifically, by adding 2.0 wt% PG@UIO, the flexural strength is increased by 50.3 %. This work enables a new paradigm for fabricating fire-safe polymer composites with the judicious design of MOFs based flame retardant.

Metal–organic frameworks and their composites: Design, synthesis, properties, and energy storage applications

Porous crystalline metal–organic frameworks (MOFs) are promising materials for supercapacitors (SCs) owing to their excellent pore structures, large surface areas, adjustable topological types, and multivalent active metal nodes, which endow them with ideal energy-storage performance. However, despite their successful application in many fields such as catalysis, gas adsorption and separation, and sensors, various intrinsic defects have hindered their practical application in SCs. In recent years, MOFs have demonstrated significant advancements in their electrochemical performance, and their applications in SCs have been gaining momentum. This review summarizes the design, classification, synthesis strategies, and properties of MOFs. The formation conditions and mechanisms of MOFs are discussed and the effects of the different types and synthesis strategies of MOFs on their properties are compared to improve their design and preparation. The research progress on pristine MOFs and their composites in SCs is reviewed, highlighting the solutions for the intrinsic defects in pristine MOFs in SC applications. The challenges of utilizing MOF-based materials in SC applications are summarized and potential solutions for their future development are suggested.

Enabling long-distance hydrogen spillover in nonreducible metal-organic frameworks for catalytic reaction

Hydrogen spillover is an extraordinary effect in heterogeneous catalysis and hydrogen storage, which refers to the surface migration of metal particle-activated hydrogen atoms over the solid supports. Historical studies on this phenomenon have mostly been limited to reducible metal oxides where the long-distance proton-electron coupled migration mechanism has been established, yet the key question remains on how to surmount short-distance and defect-dependent hydrogen migration on nonreducible supports. By demerging hydrogen migration and hydrogenation reaction, here we demonstrate that the hydrogen spillover in nonreducible metal-organic frameworks (MOFs) can be finely modulated by the ligand functional groups or embedded water molecules, enabling significant long-distance (exceed 50 nm) movement of activated hydrogen. Furthermore, using sandwich nanostructured MOFs@Pt@MOFs as catalysts, we achieve highly selective hydrogenation of N-heteroarenes via controllable hydrogen spillover from Pt to MOFs-shell. We anticipate that this work will enhance the understanding of hydrogen spillover and shed light on de novo design of MOFs supported catalysts for many important reactions involving hydrogen.

Metal–organic frameworks for nonlinear optics and lasing

AbstractNonlinear optics (NLO) is a crucial branch of photonics that greatly facilitates the transmission, processing, and storage of photonic signals. It meets the needs of the rapidly growing information demands of modern society. Materials with NLO properties and laser capabilities have a wide range of applications in fields such as optical communication, optical information storage, biomedical imaging, laser technology, and quantum information technology. Metal–organic frameworks (MOFs) have emerged as particularly exciting hybrid inorganic–organic porous materials that can be easily self‐assembled from corresponding inorganic metal ions/clusters and organic linkers. The structural diversity and flexibility of MOFs offer ample opportunities for the orderly organization of highly hyperpolarizable chromophore molecules within confined spaces. This makes it ideal for NLO signal and laser emissions. In this review, we provide a comprehensive overview of strategies to construct MOFs with NLO and laser properties, as well as recent research developments for enhancing and adjusting these properties. Through analysis of chromophore arrangement and various interactions within the framework, we aim to gain insight into the correlation between MOF structures and optical properties. This will facilitate the design and synthesis of MOFs with excellent NLO and laser capabilities through the judicious selection of metal ions and organic linkers. Finally, we outline the future challenges and potential research directions for MOFs in NLO and laser fields.

Metal-organic frameworks and composites on their basis: structure, synthesis methods, electrochemical properties and application prospects (a review)

Various types of metal-organic frameworks (MOF) and their structural parameters have been reviewed and their classification has been presented. Most widely used synthesis methods and approaches for MOF and composites on their basis have been discussed. MOF structure is a regular 3D lattice formed by organic linkers and metallic clusters. It has been shown for an example of literary data on MOF synthesis and structural studies that the types of bonds and metals can strongly affect the spatial structure and dimensions of MOF crystals: they can have nano-, micro- and meso-dimensions, be dense or porous, bulk or layered. This variety of structural parameters determines the wide range of their properties and potential applications. Prospects and methods of controlling the shapes of the crystals, their size and spatial bonds between organic components and metal ions have been reviewed. Major attention has been paid to zeolite-like frameworks (ZIF) as the most promising ones from the viewpoint of structure, synthesis and electrochemical current source applications. Discussion has touched on possible modifications and methods of controlling the properties of those MOFs and composites on their basis and introduction of impurities, including those having magnetic properties. Possible synthesis options of complex composites through controlled MOF pyrolysis have been presented, for either small-batch or scalable processes. The effect of heat treatment conditions on the final properties and electrochemical applications of those materials has been demonstrated. ZIF-67 structured MOF doping with one more metal has been presented as variant of modifying the properties of MOF and composites on their basis. For example, the Authors have implemented cobalt MOF synthesis wherein cobalt is partially substituted for manganese at the synthesis stage. Furthermore, a simple water solution co-deposition synthesis technique has been modified with ultrasonication thus reducing the time consumption of the process. Electrochemical studies have shown that the unit electrochemical capacity of pyrolyzed MOF electrodes with partial cobalt substitution for manganese is appreciably higher as compared to the manganese-free materials. The unit capacity and energy density increase with manganese content in the MOF. MOF manganese doping delivers a considerable improvement in the electrochemical parameters of the electrode materials for hybrid supercapacitors on their basis (from 100 to 298 F/g at 0.25 A/g current density). The results suggest that cobalt substitution for manganese is an effective method of improving the electrochemical parameters of MOFs. It has been demonstrated that the development of new approaches to the design of MOF based composite materials and the study of the physicochemical regularities of their interaction with various carriers is an important task.