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, 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, , making them particularly attractive for 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.

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.

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.

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.

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.

Hierarchical conductive metal-organic framework films enabling efficient interfacial mass transfer.

Heterogeneous reactions associated with porous solid films are ubiquitous and play an important role in both nature and industrial processes. However, due to the no-slip boundary condition in pressure-driven flows, the interfacial mass transfer between the porous solid surface and the environment is largely limited to slow molecular diffusion, which severely hinders the enhancement of heterogeneous reaction kinetics. Herein, we report a hierarchical-structure-accelerated interfacial dynamic strategy to improve interfacial gas transfer on hierarchical conductive metal-organic framework (c-MOF) films.

Theoretical Study on the Swelling Mechanism and Structural Stability of NiAl-LDH Based on Molecular Dynamics.

layered double hydroxide (LDH) as a kind of 2D layer material has a swelling phenomenon. Because swelling significantly affects the adsorption, catalysis, energy storage, and other application properties of LDHs, it is essential to study the interlayer spacing, structural stability, and ion diffusion after swelling. In this paper, a periodic computational model of NiAl-LDH is constructed, and the supramolecular structure, swelling law, stability, and anion diffusion properties of NiAl-LDH are investigated by molecular dynamics theory calculations.

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 symmetry, namely, "4 + 2" phenyl ligands.

Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved.

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 CuO linking, named as Cu HHAE .

Bioinspired Neuron-like Adsorptive Networks for Heavy Metal Capture and Tunable Electrochemically Mediated Recovery.

Electrochemical techniques have garnered increasing attention as a heavy metal remediation platform for pollutant mitigation and sustainable recycling. Inspired by the biological signal-transfer mode, biomimic neuron-like hierarchical adsorptive networks were constructed by interweaving one-dimensional manganese oxide nanowires into polyaniline-decorated hollow structural metal-organic frameworks (MOFs). The prepared biomimic neuron adsorbent exhibits good adsorption capacity toward cations (Pb) and oxyanions (CrO) at the neutral state; tunable cation/oxyanion desorption can be electrochemically switched at the oxidized and reduced states, respectively, where the biomimic neuron-like hierarchical adsorptive networks facilitated electron transfer and benefited substantial redox reactions.

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.

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.

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.

Mechanical and Tribological Performances Enhanced by Self-Assembled Structures.

Taking inspiration from natural materials, composite materials can be reinforced by creating matrix architectures that can better accommodate and control internal stresses. Despite the recent success in the synthesis of artificial assemblies for local reinforcement through the introduction of oriented fibers and plates into host multilayered composites, there is a lack of fundamental understanding of the factors that determine mechanical properties. Moreover, designing building blocks and interfaces that facilitate higher resistance and energy dissipation is highly challenging.

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.

Effect of structure: A new insight into nanoparticle assemblies from inanimate to animate.

Nanoparticle (NP) assemblies are among the foremost achievements of nanoscience and nanotechnology because their interparticle interactions overcome the weaknesses displayed by individual NPs. However, previous studies have considered NP assemblies as inanimate, which had led to their dynamic properties being overlooked. Animate properties, i.

A Metal-Organic Framework Nanosheet-Assembled Frame Film with High Permeability and Stability.

The engineering of metal-organic frameworks (MOFs) into membranes and films is being investigated, to transform laboratory-synthesized MOFs into industrially viable products for a range of attractive applications. However, rational design and construction of highly permeable MOF thin films, without trade-offs in terms of structural mechanical stability, remains a significant challenge. Herein, a simple, general strategy is reported to prepare thin MOF nanosheet (NS)-assembled frame film via heteroepitaxial growth from metal hydroxide film.

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.

Optimization of Artificial Light for Spinach Growth in Plant Factory Based on Orthogonal Test.

Artificial LED source provides the possibility to regulate the lighting environment in plant factorys that use limited space to plant, aiming at high throughput and good quality. However, different parameters of light intensity, quality, and photoperiod will influence the growth and accumulation of bio-compounds in plants. In order to find the optimal setting of LED light for spinach planting, four group experiments were designed using the orthogonal testing method.

[In-situ solvothermal polymerization of metal-organic framework/carbon-nitrogen nanosheet-coated solid-phase microextraction fiber for highly sensitive detection of pesticide residues in black tea].

Pyrethroids (PYs) and organochlorine pesticides (OCPs) are widely used to control pests and diseases in plants; however, they threaten human health. In this study, a metal-organic framework/carbon-nitrogen nanosheet composite nanomaterial (UiO-66/HOCN)-coated solid-phase microextraction (SPME) fiber was prepared by in-situ thermal polymerization. The prepared UiO-66/HOCN composite material was characterized by transmission electron microscopy, X-ray diffraction, nitrogen adsorption porosimetry, thermogravimetric analysis, and zeta potentiometry.

Nanomaterial-based gas sensors used for breath diagnosis.

Gas-sensing applications commonly use nanomaterials (NMs) because of their unique physicochemical properties, including a high surface-to-volume ratio, enormous number of active sites, controllable morphology, and potential for miniaturisation. NM-based gas sensors, as a noninvasive, real-time technique, are a promising candidate for monitoring human breath. This review focuses on NM-based gas sensors used for breath diagnosis.