Conductive Metal-organic Frameworks Research Articles

Performance evaluation of a dynamic electrooxidation systems with magnetically functionalised UiO-66-NH2 and Ti/Sb–SnO2 for methotrexate treatment

Novel conductive MOF magnetic particles Fe3O4@UiO-66-NH2@PANI (FUP) were prepared and combined with Ti/Sb–SnO2 electrodes to construct a dynamic system with improved electrochemical oxidation efficiency. Electrochemical tests revealed that the Ti/Sb–SnO2–FUP electrodes showed a high active specific surface area and low charge transfer resistance. Investigation of the effects of parameters such as dynamic particle loading, magnetic separation time, initial concentration, Na2SO4 dosage and solution pH on the methotrexate (MTX) degradation rate revealed that the degradation rate reached 97.5%. Electron paramagnetic resonance spectroscopy revealed that the Ti/Sb–SnO2–FUP electrodes could produce abundant hydroxyl radicals, possibly due to the unique pore structure of UiO-66-NH2 and the semiconductor structure of aniline. Finally, the decomposition pathway of MTX and ecotoxicity of the intermediates were analysed through LC-MS/MS and Toxicity Estimation Software Tool theoretical calculations combined with genotoxicity experiments. The results showed that Ti/Sb–SnO2–FUP could effectively reduce the toxicity of the intermediates. In this work, a dynamic electrooxidation system was developed using magnetic Ti/Sb–SnO2 electrodes coupled with MOFs, providing a new idea to improve the oxidative degradation efficiency of electrooxidation systems.

Single-Atom Catalysts in Conductive Metal-Organic Frameworks: Enabling Reversible Gas Sensing at Room Temperature.

Conductive metal-organic frameworks (cMOFs) offer high porosity and electrical conductivity simultaneously, making them ideal for application in chemiresistive sensors. Recently, incorporating foreign elements such as catalytic nanoparticles into cMOFs has become a typical strategy to enhance their sensing properties. However, this approach has led to critical challenges, such as pore blockage that impedes gas diffusion, as well as limited improvement in reversibility. Herein, single-atom catalyst (SAC)-functionalized cMOF is presented as a robust solution to the current limitations. Facile functionalization of SACs in a cMOF can be achieved through electrochemical deposition of metal precursors. As a proof of concept, a Pd SAC-functionalized cMOF is synthesized. The Pd SACs are stabilized at the interplanar sites of cMOF with Pd-N4 coordination while preserving the porosity of the MOF matrix. Notably, the microenvironment created by Pd SACs prevents irreversible structural distortion of cMOFs and facilitates a reversible charge transfer with NO2. Consequently, the cMOF exhibits a fully recoverable NO2 response, which was not previously attainable with the nanoparticle functionalization. Additionally, with the combination of preserved porosity for gas diffusion, it demonstrates the fastest level of response and recovery speed compared to other 2D-cMOFs of this class.

Efficient electroreduction of CO2 to acetate with relative purity of 100% by ultrasmall Cu2O nanoparticle on a conductive metal-organic framework

Efficient electroreduction of CO2 to acetate with relative purity of 100% by ultrasmall Cu2O nanoparticle on a conductive metal-organic framework

Solution-Processable MOF-on-MOF System Constructed via Template-Assisted Growth for Ultratrace H2S Detection.

Conductive metal-organic frameworks (c-MOFs) hold promise for highly sensitive sensing systems due to their conductivity and porosity. However, the fabrication of c-MOF thin films with controllable morphology, thickness, and preferential orientation remains a formidable yet ubiquitous challenge. Herein, we propose an innovative template-assisted strategy for constructing MOF-on-MOF (Ni3(HITP)2/NUS-8 (HITP: 2,3,6,7,10,11-hexamino-tri(p-phenylene))) systems with good electrical conductivity, porosity, and solution processability. Leveraging the 2D nature and solution processability of NUS-8, we achieve the controllable self-assembly of Ni3(HITP)2 on NUS-8 nanosheets, producing solution-processable Ni3(HITP)2/NUS-8 nanosheets with a film conductivity of 1.55 × 10-3 S·cm-1 at room temperature. Notably, the excellent solution processability facilitates the fabrication of large-area thin films and printing of intricate patterns with good uniformity, and the Ni3(HITP)2/NUS-8-based system can monitor finger bending. Gas sensors based on Ni3(HITP)2/NUS-8 exhibit high sensitivity (LOD ~ 6 ppb) and selectivity towards ultratrace H2S at room temperature, attributed to the coupling between Ni3(HITP)2 and NUS-8 and the redox reaction with H2S. This approach not only unlocks the potential of stacking different MOF layers in a sequence to generate functionalities that cannot be achieved by a single MOF, but also provides novel avenues for the scalable integration of MOFs in miniaturized devices with salient sensing performance.

Electrodeposition of Ni/Cu Bimetallic Conductive Metal-Organic Frameworks Electrocatalysts with Boosted Oxygen Reduction Activity for Zinc-Air Batteries.

Zinc-air batteries employing non-Pt cathodes hold significant promise for advancing cathodic oxygen reduction reaction (ORR). However, poor intrinsic electrical conductivity and aggregation tendency hinder the application of metal-organic frameworks (MOFs) as active ORR cathodes. Conductive MOFs possess various atomically dispersed metal centers and well-aligned inherent topologies, eliminating the additional carbonization processes for achieving high conductivity. Here, a novel room-temperature electrochemical cathodic electrodeposition method is introduced for fabricating uniform and continuous layered 2D bimetallic conductive MOF films cathodes without polymeric binders, employing the organic ligand 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and varying the Ni/Cu ratio. The influence of metal centers on modulating the ORR performance is investigated by density functional theory (DFT), demonstrating the performance of bimetallic conductive MOFs can be effectively tuned by the unpaired 3d electrons and the Jahn-Teller effect in the doped Cu. The resulting bimetallic Ni2.1Cu0.9(HITP)2 exhibits superior ORR performance, boasting a high onset potential of 0.93V. Moreover, the assembled aqueous zinc-air battery demonstrates high specific capacity of 706.2mA h g-1, and exceptional long-term charge/discharge stability exceeding 1250 cycles.

Vertical Conductive Metal-Organic Framework Single-Crystalline Nanowire Arrays for Efficient Electrocatalytic Hydrogen Evolution.

The construction of crystalline metal-organic frameworks with regular architectures supportive of enhanced mass transport and bubble diffusion is imperative for electrocatalytic applications; however, this poses a formidable challenge. Here, a method is presented that confines the growth of nano-architectures to the liquid-liquid interface. Using this method, vertically oriented single crystalline nanowire arrays of an Ag-benzenehexathiol (BHT) conductive metal-organic framework (MOF) are fabricated via an "in-plane self-limiting and out-of-plane epitaxial growth" mechanism. This material has excellent electrocatalytic features, including highly exposed active sites, intrinsically high electrical conductivity, and superhydrophilic and superaerophobic properties. Leveraging these advantages, the carefully designed material demonstrates superior electrocatalytic hydrogen evolution activity, resulting in a low Tafel slope of 66mVdec-1 and a low overpotential of 275mV at a high current density of 1Acm-2. Finite element analysis (FEA) and in situ microscopic verification indicates that the nanowire array structure significantly enhances the electrolyte transport kinetics and promotes the rapid release of gas bubbles. The findings highlight the potential of using MOF-based ordered nanoarray structures for advanced electrocatalytic applications.

Revealing Ion Adsorption and Charging Mechanisms in Layered Metal-Organic Framework Supercapacitors with Solid-State Nuclear Magnetic Resonance.

Conductive layered metal-organic frameworks (MOFs) have demonstrated promising electrochemical performances as supercapacitor electrode materials. The well-defined chemical structures of these crystalline porous electrodes facilitate structure-performance studies; however, there is a fundamental lack in the molecular-level understanding of charge storage mechanisms in conductive layered MOFs. To address this, we employ solid-state nuclear magnetic resonance (NMR) spectroscopy to study ion adsorption in nickel 2,3,6,7,10,11-hexaiminotriphenylene, Ni3(HITP)2. In this system, we find that separate resonances can be observed for the MOF's in-pore and ex-pore ions. The chemical shift of in-pore electrolyte is found to be dominated by specific chemical interactions with the MOF functional groups, with this result supported by quantum mechanics/molecular mechanics (QM/MM) and density functional theory (DFT) calculations. Quantification of the electrolyte environments by NMR was also found to provide a proxy for electrochemical performance, which could facilitate the rapid screening of synthesized MOF samples. Finally, the charge storage mechanism was explored using a combination of ex-situ NMR and operando electrochemical quartz crystal microbalance (EQCM) experiments. These measurements revealed that cations are the dominant contributors to charge storage in Ni3(HITP)2, with anions contributing only a minor contribution to the charge storage. Overall, this work establishes the methods for studying MOF-electrolyte interactions via NMR spectroscopy. Understanding how these interactions influence the charging storage mechanism will aid the design of MOF-electrolyte combinations to optimize the performance of supercapacitors, as well as other electrochemical devices including electrocatalysts and sensors.

Integrating Electrochemical Analysis and Machine Learning for Enhanced Discovery of Conductive MOFs: A Database-Driven Approach

Metal-organic frameworks (MOFs) are highly versatile structures composed of metal ions linked by organic molecules. They offer a broad range of applications in electronics and light-based technologies due to their flexibility. However, the connection between metal ions and organic components often hinders efficient charge movement, which is essential for electrical conduction. To address this challenge, researchers have been innovatively designing MOFs to enhance their conductivity, which is typically low. This process is complex and time-consuming. To overcome these barriers, and to save both time and costs, we integrated machine learning (ML) with electrochemical testing. Our aim was to pinpoint ion and electron conductive MOFs from the Computation-Ready, Experimental Metal–Organic Framework (CoREMOF) Database, which contains over 14,000 MOFs. The ML approach predicted 84 intrinsically conductive MOFs, which were then subjected to rigorous experimental validation through synthesis and conductivity performance testing. Further experimental data confirmed that only two conductive MOFs, containing copper and pyrazole structures with carbonyl groups, exhibited both proton and electron conductivity. The differences between them lie solely in the preparation techniques and solvents used. Sample 1 was prepared using hydrothermal methods and alcohol as the solvent, and NH4@1 was prepared with an ammonium solution at room temperature. To understand deeper their intrinsic conductivity and semiconductor properties, we employed temperature-dependent conductivity and electrochemical measurements, including Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS), Linear Sweep Voltammetry (I-V), and Mott-Schottky analysis. The EIS data showed a smaller semicircular arc for synthesized NH4@1, indicating its lower charge transfer resistance due to the presence of two different positive charge carriers on its surface. We investigated the effect of increasing positive charge carriers by raising the humidity up to 98% RH. EIS data showed that increasing positive charge has a significantly reduced charge transfer resistance of sample 1 compared to NH4@1. Because NH4@1 consists of ammonium and H3O+ simultaneously, causing saturation of positive charges and increasing charge transfer resistance. Mott-Schottky analysis further elucidated the electrical properties of compounds 1 and NH4@1, revealing their p-type behavior with negative slopes and flat band potentials of 0.61 V and 0.9 V, respectively. The CV analysis of pyrazole carboxylic acid in a 0.1 M KOH solution, using three reference electrodes, revealed reduction and oxidation peaks vs. Ag/AgCl. These peaks highlight the redox behavior of the linker, generating a stable carboxylate anion (-COO−) that facilitates charge hopping. This reversible redox activity is crucial for the charge transport mechanism within the MOFs. CV analyses confirmed the presence of different copper oxidation states in both compounds, with cathodic peaks indicating the reduction from Cu(II) to Cu(I), suggesting active charge transfer. Extensive electrochemical studies, encompassing both Mott-Schottky and EIS analyses, provided deeper insights into charge carriers and transfer resistance, areas not extensively explored in previous research on intrinsically conductive MOFs. Our results underscore the critical role of experimental validation of ML predictions in accelerating the discovery and characterization of conductive MOFs for potential applications in batteries.

(Invited) Diverse Strategies for Pseudocapacitance in 2D Materials and Beyond

As electronic technology advances, the need in safe and long-lasting energy storage devices that occupy minimum volume arises. Short charging times of several seconds to minutes, with energy densities comparable to those of batteries, can be achieved in pseudocapacitors. These are sub-class of supercapacitors, where capacitance is mediated by fast redox reactions and can enable at least an order of magnitude more energy to be stored than in typical electrical double layer capacitors. Transition metal oxides (e.g. RuO2, MnO2) and conducting polymers (e.g. polyaniline) serve as typical examples. However, these materials are often high in cost and/or suffer from low cycling stability. As a result, the search for new pseudocapacitive materials constitutes an important direction today.In my talk, I will discuss various strategies to improve the performance metrics of pseudocapacitors, specifically focusing on enhancing capacitance and charging rates. I will primarily discuss the electrochemical behavior of layered materials, such as 2D transition metal carbides (MXenes) and 2D pi-conjugated conductive metal-organic frameworks, with a strong emphasis on understanding the mechanisms of charge storage and the various factors influencing electrochemical performance. Additionally, I will explore the role of cation intercalation in layered MXenes as a means to finely tune their electrochemical responses.

Advancing Electrically Conductive Metal-Organic Frameworks for Photocatalytic Energy Conversion.

ConspectusPhotocatalytic energy conversion is a pivotal process for harnessing solar energy to produce chemicals and presents a sustainable alternative to fossil fuels. Key strategies to enhance photocatalytic efficiency include facilitating mass transport and reactant adsorption, improving light absorption, and promoting electron and hole separation to suppress electron-hole recombination. This Account delves into the potential advantages of electrically conductive metal-organic frameworks (EC-MOFs) in photocatalytic energy conversion and examines how manipulating electronic structures and controlling morphology and defects affect their unique properties, potentially impacting photocatalytic efficiency and selectivity. Moreover, with a proof-of-concept study of photocatalytic hydrogen peroxide production by manipulating the EC-MOF's electronic structure, we highlight the potential of the strategies outlined in this Account.EC-MOFs not only possess porosity and surface areas like conventional MOFs, but exhibit electronic conductivity through d-p conjugation between ligands and metal nodes, enabling effective charge transport. Their narrow band gaps also allow for visible light absorption, making them promising candidates for efficient photocatalysts. In EC-MOFs, the modular design of metal nodes and ligands allows fine-tuning of both the electronic structure and physical properties, including controlling the particle morphology, which is essential for optimizing band positions and improving charge transport to achieve efficient and selective photocatalytic energy conversion.Despite their potential as photocatalysts, modulating the electronic structure or controlling the morphology of EC-MOFs is nontrivial, as their fast growth kinetics make them prone to defect formation, impacting mass and charge transport. To fully leverage the photocatalytic potential of EC-MOFs, we discuss our group's efforts to manipulate their electronic structures and develop effective synthetic strategies for morphology control and defect healing. For tuning electronic structures, diversifying the combinations of metals and linkers available for EC-MOF synthesis has been explored. Next, we suggest that synthesizing ligand-based solid solutions will enable continuous tuning of the band positions, demonstrating the potential to distinguish between photocatalytic reactions with similar redox potentials. Lastly, we present incorporating a donor-acceptor system in an EC-MOF to spatially separate photogenerated carriers, which could suppress electron-hole recombination. As a synthetic strategy for morphology control, we demonstrated that electrosynthesis can modify particle morphology, enhancing electrochemical surface area, which will be beneficial for reactant adsorption. Finally, we suggest a defect healing strategy that will enhance charge transport by reducing charge traps on defects, potentially improving the photocatalytic efficiency.Our vision in this Account is to introduce EC-MOFs as an efficient platform for photocatalytic energy conversion. Although EC-MOFs are a new class of semiconductor materials and have not been extensively studied for photocatalytic energy conversion, their inherent light absorption and electron transport properties indicate significant photocatalytic potential. We envision that employing modular molecular design to control electronic structures and applying effective synthetic strategies to customize morphology and defect repair can promote charge separation, electron transfer to potential reactants, and mass transport to realize high selectivity and efficiency in EC-MOF-based photocatalysts. This effort not only lays the foundation for the rational design and synthesis of EC-MOFs, but has the potential to advance their use in photocatalytic energy conversion.

Fabricating Large-Area Thin Films of 2D Conductive Metal-Organic Frameworks.

ConspectusRecent years have witnessed significant interest in two-dimensional metal-organic frameworks (MOFs) due to their unique properties and promising applications across various fields. These materials offer distinct advantages, including high porosity and excellent charge transport properties. Their tunability allows precise control over various factors, including the electronic structure adjustments and local reactivity modulation, facilitating a wide range of properties and applications, such as material sensing and spin dynamics control. Moreover, the precise crystal structure of 2D MOFs supports rational design and mechanism studies, providing insights into their potential applications and enhancing their utility in various scientific and technological endeavors.To fully unveil the latent capabilities of 2D MOFs and advance their applications across diverse fields, thin film synthesis is crucial. Thin films provide a platform for investigating the intrinsic electrical properties of 2D MOFs with anisotropic structures, enabling the exploration of their unique characteristics comprehensively. Additionally, thin films offer the advantage of minimizing interference at contacts and junctions, thereby enhancing the performance of 2D MOFs for various applications. Furthermore, the properties of thin films can vary with thickness, presenting an opportunity to tailor their characteristics based on specific requirements.In this Account, we present an overview of our research focusing on the synthesis of 2D conductive MOF thin films encompassing two primary methods: chemical vapor deposition and solution processing. The chemical vapor deposition method allows for one-step, all-vapor-phase processes resulting in MOFs with edge-on orientation, controllable film thicknesses ranging from 55 to 662.7 nm, and smooth, homogeneous surfaces. On the other hand, solution-processing introduces a novel MOF, Cu3(HHTATP)2, by reducing interlayer interactions through the addition of pendent Brønsted bases on a ligand, enabling spin coating for thin film synthesis. This method yields a concentrated 2D MOF solution, enabling spin coating for thin film synthesis, where reversible electrical conductivity changes occur through doping with an acid and dedoping with a base. Additionally, we discuss various other synthesis methods, such as interfacial synthesis, layer-by-layer assembly, and microfluidic-assisted synthesis, offering versatile approaches for fabricating large-area thin films with tailored properties. Finally, we address ongoing challenges and potential strategies for further advancement in 2D conductive MOF thin film synthesis. We hope that this Account provides insights for selecting synthesis methods tailored to specific purposes, contributes to the development of varied synthesis techniques, and facilitates the exploration of diverse applications, unlocking the full potential of 2D conductive MOFs for next-generation technologies.

Modeling of Nanomaterials for Supercapacitors: Beyond Carbon Electrodes.

Capacitive storage devices allow for fast charge and discharge cycles, making them the perfect complements to batteries for high power applications. Many materials display interesting capacitive properties when they are put in contact with ionic solutions despite their very different structures and (surface) reactivity. Among them, nanocarbons are the most important for practical applications, but many nanomaterials have recently emerged, such as conductive metal-organic frameworks, 2D materials, and a wide variety of metal oxides. These heterogeneous and complex electrode materials are difficult to model with conventional approaches. However, the development of computational methods, the incorporation of machine learning techniques, and the increasing power in high performance computing now allow us to tackle these types of systems. In this Review, we summarize the current efforts in this direction. We show that depending on the nature of the materials and of the charging mechanisms, different methods, or combinations of them, can provide desirable atomic-scale insight on the interactions at play. We mainly focus on two important aspects: (i) the study of ion adsorption in complex nanoporous materials, which require the extension of constant potential molecular dynamics to multicomponent systems, and (ii) the characterization of Faradaic processes in pseudocapacitors, that involves the use of electronic structure-based methods. We also discuss how recently developed simulation methods will allow bridges to be made between double-layer capacitors and pseudocapacitors for future high power electricity storage devices.

One‐Pot Synthesis of Conductive Metal–Organic Framework@polypyrrole Hybrids with Enhanced Electromagnetic Wave Absorption Performance

Rational heterostructure design can bring interfacial polarization relaxation to significantly enhance the electromagnetic wave (EMW) absorption performance. However, intelligently building a homogeneous heterostructure with superior EMW absorption properties remains a great challenge. Herein, a typical conductive metal–organic framework Cu3(HHTP)2 (hexahydroxytriphenylene, HHTP) is delicately packed onto a polypyrrole (PPy) conductive polymer surface via a one‐step in situ polymerization approach. Results show that Cu3(HHTP)2 is well packed on the PPy surface to form an elegant Cu3(HHTP)2@PPy hybrids interfacial microstructure with a unique superiority regarding EMW absorption compared with single components of PPy and Cu3(HHTP)2. Interestingly, the interfacial microstructure of Cu3(HHTP)2@PPy hybrids can be tuned by adjusting the composition of the PPy and Cu3(HHTP)2, resulting in the improvement of impedance matching, conductive loss, and enhancement of interfacial polarization relaxation, endowing the optimization of the EM wave absorption properties of the Cu3(HHTP)2@PPy. The broad effective absorption bandwidth covers a range as broad as 6.68 GHz (11.00–17.68 GHz), which is higher than most reported metal‐organic frameworks (MOFs) and conductive polymer‐based EM absorbing materials. Herein, new insight for developing highly efficient EMW absorption materials through hybridized interfacial microstructure engineering is provided.

Cellulose nanofiber-induced metal–organic framework “armor” for the fabrication of carbon fibre composites with enhanced mechanical properties and electrical conductivity

Metal-organic frameworks (MOFs) possess significant potential in enhancing the interfacial performance of composites owing to their exceptional skeletal structures and substantial specific surface area. Herein, we prepared typical conductive MOFs (Ni-HHTP, HHTP = 2, 3, 6, 7, 10, 11-hexahydroxybenzene) at the interface by in situ synthesis using cellulose nanofibers (CNFs) assembled on the surface of carbon fibres (CFs) as precursors. CNFs can not only act as a smart cushion to promote stress release but also provide abundant oxygen-containing functional groups, such as hydroxyl and carboxyl groups, which can facilitate the growth of MOF on the surface of CFs. Furthermore, MOFs with porous structure and large specific surface area increase the interphase region for interfacial load transmission. The CF composites prepared using this strategy exhibited improvements in interlaminar shear strength (ILSS), interfacial shear strength (IFSS), flexural strength and flexural modulus by 57.9 %, 54.9 %, 35.1 % and 46.7 %, respectively. Additionally, the electrical conductivities of the composites in both thickness and in-plane directions were 1.04 × 10−4 S/cm and 7.3770 S/cm, respectively, which was attributed to the MOFs on the surface of the fibres facilitating the formation of good conductive channels between the fibres and resin. This study proposes an advanced interfacial modification approach to prepare CF composites with excellent mechanical and electrical conductivity properties.

Electrochemical Anion Sensing Using Conductive Metal-Organic Framework Nanocrystals with Confined Pores.

Anion sensing technology is motivated by the widespread and critical roles played by anions in biological systems and the environment. Electrochemical approaches comprise a major portion of this field but so far have relied on redox-active molecules appended to electrodes that often lack the ability to produce mixtures of distinct signatures from mixtures of different anions. Here, nanocrystalline films of the conductive metal-organic framework (MOF) Cr(1,2,3-triazolate)2 are used to differentiate anions based on size, which consequently affect the reversible oxidation of the MOF. During framework oxidation, the intercalation of larger charge-balancing anions (e.g., ClO4-, PF6-, and OTf-) gives rise to redox potentials shifted anodically by hundreds of mV due to the additional work of solvent reorganization and anion desolvation. Smaller anions (e.g., BF4-) may enter partially solvated, while larger ansions (e.g., OTf-) intercalate with complete desolvation. As a proof-of-concept, we leverage this "nanoconfinement" approach to report an electrochemical ClO4- sensor in aqueous media that is recyclable, reusable, and sensitive to sub-100-nM concentrations. Taken together, these results exemplify an unusual combination of distinct external versus internal surface chemistry in MOF nanocrystals and the interfacial chemistry they enable as a novel supramolecular approach for redox voltammetric anion sensing.

Metal and ligand modification modulates the electrocatalytic HER, OER, and ORR activity of 2D conductive metal-organic frameworks

Metal and ligand modification modulates the electrocatalytic HER, OER, and ORR activity of 2D conductive metal-organic frameworks

Electrosynthesis of urea by using Fe2O3 nanoparticles encapsulated in a conductive metal–organic framework

Electrosynthesis of urea by using Fe2O3 nanoparticles encapsulated in a conductive metal–organic framework

Humidity-Mediated Dual Ionic-Electronic Conductivity Enables High Sensitivity in MOF Chemiresistors.

In the presence of water, the electrically conductive metal-organic framework (MOF) Cu3HHTT2 (H6HHTT = 2,3,7,8,12,13-hexahydroxy-4b1,5,10,15-tetraazanaphtho[1,2,3-gh]tetraphene) provides a conduit for proton transport, thereby becoming a dual ionic-electronic conductor. Owing to its dual conducting nature and its high density of imine and open metal sites, the MOF operates as a particularly sensitive chemiresistor, whose sensing mechanism changes with relative humidity. Thus, the interaction of NH3 gas with the MOF under low humidity promotes proton transport, which translates to high sensitivity for ammonia detection. Conversely, NO2 gas hinders proton conductivity, even under high relative humidity conditions, leading to large resistance variations in the humid regime. This dual ionic-electronic conduction-based gas sensor provides superior sensitivity compared to other conventional chemiresistors under similar conditions and highlights its potential as a platform for room-temperature gas sensors.

Preparation of W-N-C single atom catalyst and Cu3(HHTP)2 metal-organic framework dual-decorated graphene nanoplatelet flexible electrode arrays for the rapid detection of carbendazim in vegetables

It is highly desirable to develop a low-cost and rapid detection method for trace levels of carbendazim fungicide residues, which would be beneficial for improving human health and mitigating environmental issues. Herein, isolated single tungsten atoms were implanted onto well-organized metal–organic framework (MOF)-derived N-doped carbons to form W-N-C single-site heterojunctions with ultrahigh electrocatalytic activity. The coupling of W-N-C with Cu3(HHTP)2, an electronically conductive MOF with a large surface area and porous structure, exhibited enhanced electrocatalytic performance for the oxidation of carbendazim (CBZ) when they were used for decorating graphene nanoplatelet flexible electrode arrays fabricated via template-assisted scalable filtration. A wide linear range (3.0 nM–50 μM) with an ultra-low detection limit of 0.97 nM and fast response was achieved for CBZ analysis. Moreover, the sensing platform has been utilised to monitor CBZ levels in vegetable samples with satisfactory recovery rates of 97.2–102% and a low relative standard deviation of 1.9%.

Activation of MOF Catalysts with Low Steric Hindrance via Undercoordination Chemistry for Efficient Polysulfide Conversion in Lithium–Sulfur Battery

AbstractLithium–sulfur (Li–S) batteries promise high theoretical energy density and cost‐effectiveness but grapple with challenges like the polysulfide shuttle effect and sluggish kinetics. Metal–organic framework (MOF) catalysts emerge as a leading solution, despite limited conductivity and high steric hindrance. This study employs undercoordination chemistry to modify Zn–Co bimetallic MOFs (D‐ZIF L), removing organic ligands from active centers. This process mitigates spatial hindrance, thereby promoting comprehensive contact between sulfur species and metal active centers, consequently enhancing the catalytic efficiency of MOFs. Moreover, undercoordination treatment of the metal active centers induces electron redistribution, augmenting electron density at the Fermi level of the metal elements, thereby ameliorating the intrinsic conductivity. Leveraging these advantages, fabricated Li–S batteries employing D‐ZIF L catalysts exhibited markedly mitigated shuttling effects and accelerated sulfur species conversion kinetics. Notably, a substantial reverse areal capacity of 5.0 mAh cm⁻2 is achieved after 100 cycles with an evaluated sulfur loading of 5.5 mg cm⁻2. Furthermore, a practical pouch cell demonstrated an initial capacity of 1.8 Ah at 85.8 mA with stable cycling for 50 cycles. This study underscores the potential of undercoordination chemistry in the development of highly conductive MOF catalysts with minimized steric hindrance, thereby advancing the prospects of Li–S battery technology.