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The effect of humidity on the cooperative adsorption of CO2 from the air on amine-appended metal–organic frameworks is studied both experimentally and theoretically. Breakthrough experiments show that, at low relative humidities, there is an anomalous induction effect, where the kinetics at short times are slower than kinetics at long times. The induction effect gradually vanishes as relative humidity is increased, corresponding to an increase in CO2 adsorption rate. A new theory is proposed based on the lattice kinetic theory (LKT), which explains these experimental results. LKT can accurately represent the measured data over the full range of humidities by postulating that the presence of adsorbed water shifts the equilibrium clusters from cooperatively bound chains to non-cooperatively bound CO2. A consequence of this transition is that CO2 exhibits step adsorption isotherm in dry air and a standard Langmuir adsorption isotherm in high humidity air. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) are promising candidate materials for photo-driven processes. Their crystalline and tunable structure makes them well-suited for placing photoactive molecules at controlled distances and orientations that support processes such as light harvesting and photocatalysis. In order to optimize their performance, it is important to understand how these molecules evolve shortly after photoexcitation. Here, we use resonance Raman intensity analysis (RRIA) to quantify the excited state nuclear distortions of four modified UiO-68 MOFs. We find that stretching vibrations localized on the central ring within the terphenyl linker are most distorted upon interaction with light. We use a combined computational and experimental approach to create a picture of the early excited state structure of the MOFs upon photoactivation. Overall, we show that RRIA is an effective method to probe the excited state structure of photoactive MOFs and can guide the synthesis and optimization of photoactive designs. [ABSTRACT FROM AUTHOR]

The chemical flexibility of metal-organic frameworks (MOFs) offers an ideal platform to tune structure and composition for specific applications, from gas sensing to catalysis and from photoelectric conversion to energy storage. This variability gives rise to a large configurational space that can be efficiently explored using high-throughput computational methods. In this work, we investigate from first principles the structural and electronic properties of MOF-5 variants obtained by replacing Zn with Be, Mg, Cd, Ca, Sr, and Ba and by functionalizing the originally H-passivated linkers with CH3, NO2, Cl, Br, NH2, OH, and COOH groups. To build and analyze the resulting 56 structures, we employ density-functional theory calculations embedded in an in-house developed library for automatized calculations. Our findings reveal that structural properties are mainly defined by metal atoms and large functional groups, which distort the lattice and modify coordination. The formation energy is largely influenced by functionalization and enhanced by COOH and OH groups, which promote the formation of hydrogen bonds. The charge distribution within the linker is especially influenced by functional groups with electron-withdrawing properties, while the metal nodes play a minor role. Likewise, the bandgap size is crucially determined by ligand functionalization. The smallest gaps are found with NH2 and OH groups, which introduce localized orbitals at the top of the valence band. This characteristic makes these functionalizations particularly promising for the design of MOF-5 variants with enhanced gas uptake and sensing properties. [ABSTRACT FROM AUTHOR]

This study introduces recommendations for conducting molecular simulations of vapor adsorption, with an emphasis on enhancing the accuracy, reproducibility, and comparability of results. The first aspect we address is consistency in the implementation of some details of typical molecular models, including tail corrections and cutoff distances, due to their significant influence on generated data. We highlight the importance of explicitly calculating the saturation pressures at relevant temperatures using methods such as Gibbs ensemble Monte Carlo simulations and illustrate some pitfalls in extrapolating saturation pressures using this method. For grand canonical Monte Carlo (GCMC) simulations, the input fugacity is usually calculated using an equation of state, which often requires the critical parameters of the fluid. We show the importance of using critical parameters derived from the simulation with the same model to ensure internal consistency between the simulated explicit adsorbate phase and the implicit bulk phase in GCMC. We show the advantages of presenting isotherms on a relative pressure scale to facilitate easier comparison among models and with experiment. Extending these guidelines to a practical case study, we evaluate the performance of various isoreticular metal–organic frameworks (MOFs) in adsorption cooling applications. This includes examining the advantages of using propane and isobutane as working fluids and identifying MOFs with a superior performance. [ABSTRACT FROM AUTHOR]

When using metal–organic frameworks (MOFs) as electric field-dependent sensor devices, understanding their dielectric response is crucial as the orientation of polar groups is largely affected by confinement. To shed light on this at the molecular level, the response to a static field was computationally investigated for two structurally related MOFs, depending on their loading with guest molecules. The pillared-layer MOFs differ in their pillar moiety, with one bearing a rotatable permanent dipole moment and the other being non-polar. Two guest molecules with and without polarity, namely, methanol and methane, were considered. A comprehensive picture of the response of the guest molecules could be achieved with respect to both the amount and polarity of the confined species. For both MOFs, the dielectric response is very sensitive to the introduction of methanol, showing an anisotropic and non-linear increase in the system's relative permittivity expressed by a strongly increasing polarization response to external electric fields scaling with the number of confined methanol molecules. As expected, the effect of methane in the non-dipolar MOF is negligible, whereas subtle differences can be observed for the dipolar response of the MOF with rotatable dipolar linker groups. Taking advantage of these anisotropic and guest-molecule-specific confinement effects may open pathways for future sensing applications. Finally, methanol-induced global framework dynamics were observed in both MOFs. [ABSTRACT FROM AUTHOR]

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4′-dioxidobiphenyl-3,3′-dicarboxylate)—henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn—is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew–Burke–Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential's (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections. [ABSTRACT FROM AUTHOR]

In the pursuit of sustainable energy solutions, the development of materials with efficient hydrogen and methane storage capacities is imperative, particularly for advancing hydrogen-powered vehicles. Metal–organic frameworks (MOFs) have emerged as promising candidates to meet the stringent targets set by the Department of Energy for both hydrogen and methane storage. This study employs Grand Canonical Monte Carlo simulations to investigate the usable hydrogen and methane gravimetric and volumetric storage capacities of the recently synthesized SIGSUA. A comparative analysis encompasses the selected MOFs with similar metal compositions, those with comparable density and average pore radius, and classical benchmarks, such as IRMOF-15 and IRMOF-20, all evaluated at room temperature and moderate pressures ranging from 25 to 35 MPa. The results reveal that SIGSUA demonstrates noteworthy gravimetric and volumetric storage capacities for both hydrogen and methane, rivaling or surpassing those of the selected MOFs for analysis. These findings underscore the potential of SIGSUA in advancing clean energy storage technologies. [ABSTRACT FROM AUTHOR]

While computational screening with density functional theory (DFT) is frequently employed for the screening of metal–organic frameworks (MOFs) for gas separation and storage, commonly applied generalized gradient approximations (GGAs) exhibit self-interaction errors, which hinder the predictions of adsorption energies. We investigate the Hubbard U parameter to augment DFT calculations for full periodic MOFs, targeting a more precise modeling of gas molecule–MOF interactions, specifically for N2, CO2, and O2. We introduce a calibration scheme for the U parameter, which is tailored for each MOF, by leveraging higher-level calculations on the secondary building unit (SBU) of the MOF. When applied to the full periodic MOF, the U parameter calibrated against hybrid HSE06 calculations of SBUs successfully reproduces hybrid-quality calculations of the adsorption energy of the periodic MOF. The mean absolute deviation of adsorption energies reduces from 0.13 eV for a standard GGA treatment to 0.06 eV with the calibrated U, demonstrating the utility of the calibration procedure when applied to the full MOF structure. Furthermore, attempting to use coupled cluster singles and doubles with perturbative triples calculations of isolated SBUs for this calibration procedure shows varying degrees of success in predicting the experimental heat of adsorption. It improves accuracy for N2 adsorption for cases of overbinding, whereas its impact on CO2 is minimal, and ambiguities in spin state assignment hinder consistent improvements of O2 adsorption. Our findings emphasize the limitations of cluster models and advocate the use of full periodic MOF systems with a calibrated U parameter, providing a more comprehensive understanding of gas adsorption in MOFs. [ABSTRACT FROM AUTHOR]

The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal–organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C–H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production. [ABSTRACT FROM AUTHOR]

Polymers, known for their lightweight, high strength, and ease of processing, serve as a key component in engineering materials. Polymers with high thermal conductivity (TC) present enormous potential applications in thermal management for high-performance electronic devices. However, the discovery of thermally conductive polymers is still in a time-consuming and labor-intensive trial-and-error process, which undoubtedly hinders the progress in related applications. Fortunately, machine learning (ML) enables to overcome this obstacle by building precise models to predict the TC of polymers through learning from a large volume of data and it can quickly identify polymers with high TC and provide significant insights to guide further design and innovation. In this mini review, we briefly describe the general process of using ML to predict polymers with high TC and then give guidance for the selection and utilization of three important components: database, descriptor, and algorithm. Furthermore, we summarize the predicted thermally conductive single polymer chains, amorphous polymers, and metal-organic frameworks via ML and identify the key factors that lead to high TC. Finally, we touch on the challenges faced when utilizing ML to predict the TC of polymer and provide a foresight into future research endeavors. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs), with their unique porous structures and versatile functionality, have emerged as promising materials for the adsorption, separation, and storage of diverse molecular species. In this study, we investigate water adsorption in MOF-808, a prototypical MOF that shares the same secondary building unit (SBU) as UiO-66, and elucidate how differences in topology and connectivity between the two MOFs influence the adsorption mechanism. To this end, molecular dynamics simulations were performed to calculate several thermodynamic and dynamical properties of water in MOF-808 as a function of relative humidity (RH), from the initial adsorption step to full pore filling. At low RH, the μ3-OH groups of the SBUs form hydrogen bonds with the initial water molecules entering the pores, which triggers the filling of these pores before the μ3-OH groups in other pores become engaged in hydrogen bonding with water molecules. Our analyses indicate that the pores of MOF-808 become filled by water sequentially as the RH increases. A similar mechanism has been reported for water adsorption in UiO-66. Despite this similarity, our study highlights distinct thermodynamic properties and framework characteristics that influence the adsorption process differently in MOF-808 and UiO-66. [ABSTRACT FROM AUTHOR]

Despite the intense activity at electronic and atomistic resolutions, coarse grained (CG) modeling of metal–organic frameworks remains largely unexplored. One of the main reasons for this is the lack of adequate CG force fields. In this work, we present iterative Boltzmann inversion and force matching (FM) force fields for modeling ZIF-8 at three different coarse grained resolutions. Their ability to reproduce structure, elastic tensor, and thermal expansion is evaluated and compared with that of MARTINI force fields considered in previous work [Alvares et al., J. Chem. Phys. 158, 194107 (2023)]. Moreover, MARTINI and FM are evaluated for their ability to depict the swing effect, a subtle phase transition ZIF-8 undergoes when loaded with guest molecules. Overall, we found that all our force fields reproduce structure reasonably well. Elastic constants and volume expansion results are analyzed, and the technical and conceptual challenges of reproducing them are explained. Force matching exhibits promising results for capturing the swing effect. This is the first time these CG methods, widely applied in polymer and biomolecule communities, are deployed to model porous solids. We highlight the challenges of fitting CG force fields for these materials. [ABSTRACT FROM AUTHOR]

The intensifying global opioid crisis, majorly attributed to fentanyl (FT) and its analogs, has necessitated the development of rapid and ultrasensitive remote/on-site FT sensing modalities. However, current approaches for tracking FT exposure through wastewater-based epidemiology (WBE) are unadaptable, time-consuming, and require trained professionals. Toward developing an extended in situ wastewater opioid monitoring system, we have developed a screen-printed electrochemical FT sensor and integrated it with a customized submersible remote sensing probe. The sensor composition and design have been optimized to address the challenges for extended in situ FT monitoring. Specifically, ZIF-8 metal-organic framework (MOF)-derived mesoporous carbon (MPC) nanoparticles (NPs) are incorporated in the screen-printed carbon electrode (SPCE) transducer to improve FT accumulation and its electrocatalytic oxidation. A rapid (10 s) and sensitive square wave voltammetric (SWV) FT detection down to 9.9 µgL-1 is thus achieved in aqueous buffer solution. A protective mixed-matrix membrane (MMM) has been optimized as the anti-fouling sensor coating to mitigate electrode passivation by FT oxidation products and enable long-term, intermittent FT monitoring. The unique MMM, comprising an insulating polyvinyl chloride (PVC) matrix and carboxyl-functionalized multi-walled carbon nanotubes (CNT-COOH) as semiconductive fillers, yielded highly stable FT sensor operation (> 95% normalized response) up to 10 h in domestic wastewater, and up to 4 h in untreated river water. This sensing platform enables wireless data acquisition on a smartphone via Bluetooth. Such effective remote operation of submersible opioid sensing probes could enable stricter surveillance of community water systems toward timely alerts, countermeasures, and legal enforcement.

Interactions among biomacromolecules, predominantly noncovalent, underpin biological processes. However, recent advancements in biospecific chemistry have enabled the creation of specific covalent bonds between biomolecules, both in vitro and in vivo. This Review traces the evolution of biospecific chemistry in proteins, emphasizing the role of genetically encoded latent bioreactive amino acids. These amino acids react selectively with adjacent natural groups through proximity-enabled bioreactivity, enabling targeted covalent linkages. We explore various latent bioreactive amino acids designed to target different protein residues, ribonucleic acids, and carbohydrates. We then discuss how these novel covalent linkages can drive challenging protein properties and capture transient protein-protein and protein-RNA interactions in vivo. Additionally, we examine the application of covalent peptides as potential therapeutic agents and site-specific conjugates for native antibodies, highlighting their capacity to form stable linkages with target molecules. A significant focus is placed on proximity-enabled reactive therapeutics (PERx), a pioneering technology in covalent protein therapeutics. We detail its wide-ranging applications in immunotherapy, viral neutralization, and targeted radionuclide therapy. Finally, we present a perspective on the existing challenges within biospecific chemistry and discuss the potential avenues for future exploration and advancement in this rapidly evolving field.

In this study, we used a high-throughput computational screening approach to examine the potential of metal–organic frameworks (MOFs) for capturing propane (C3H8) from different gas mixtures. We focused on Quantum MOF (QMOF) database composed of both synthesized and hypothetical MOFs and performed Grand Canonical Monte Carlo (GCMC) simulations to compute C3H8/N2/O2/Ar and C3H8/C2H6/CH4 mixture adsorption properties of MOFs. The separation of C3H8 from air mixture and the simultaneous separation of C3H8 and C2H6 from CH4 were studied for six different adsorption-based processes at various temperatures and pressures, including vacuum-swing adsorption (VSA), pressure-swing adsorption (PSA), vacuum–temperature swing adsorption (VTSA), and pressure-temperature swing adsorption (PTSA). The results of molecular simulations were used to evaluate the MOF adsorbents and the type of separation processes based on selectivity, working capacity, adsorbent performance score, and regenerability. Our results showed that VTSA is the most effective process since many MOFs offer high regenerability (>90%) combined with high C3H8 selectivity (>7 × 103) and high C2H6 + C3H8 selectivity (>100) for C3H8 capture from air and natural gas mixtures, respectively. Analysis of the top MOFs revealed that materials with narrow pores (<10 Å) and low porosities (<0.7), having aromatic ring linkers, alumina or zinc metal nodes, typically exhibit a superior C3H8 separation performance. The top MOFs were shown to outperform commercial zeolite, MFI for C3H8 capture from air, and several well-known MOFs for C3H8 capture from natural gas stream. These results will direct the experimental efforts to the most efficient C3H8 capture processes by providing key molecular insights into selecting the most useful adsorbents. [ABSTRACT FROM AUTHOR]

Zeolitic imidazolate frameworks (ZIFs) feature complex phase transitions, including polymorphism, melting, vitrification, and polyamorphism. Experimentally probing their structural evolution during transitions involving amorphous phases is a significant challenge, especially at the medium-range length scale. To overcome this challenge, here we first train a deep learning-based force field to identify the structural characteristics of both crystalline and non-crystalline ZIF phases. This allows us to reproduce the structural evolution trend during the melting of crystals and formation of ZIF glasses at various length scales with an accuracy comparable to that of ab initio molecular dynamics, yet at a much lower computational cost. Based on this approach, we propose a new structural descriptor, namely, the ring orientation index, to capture the propensity for crystallization of ZIF-4 (Zn(Im)2, Im = C3H3N2-) glasses, as well as for the formation of ZIF-zni (Zn(Im)2) out of the high-density amorphous phase. This crystal formation process is a result of the reorientation of imidazole rings by sacrificing the order of the structure around the zinc-centered tetrahedra. The outcomes of this work are useful for studying phase transitions in other metal-organic frameworks (MOFs) and may thus guide the development of MOF glasses.

Nanoporous materials are of great interest in many applications, such as catalysis, separation, and energy storage. The performance of these materials is closely related to their pore sizes, which are inefficient to determine through the conventional measurement of gas adsorption isotherms. Nuclear magnetic resonance (NMR) relaxometry has emerged as a technique highly sensitive to porosity in such materials. Nonetheless, streamlined methods to estimate pore size from NMR relaxometry remain elusive. Previous attempts have been hindered by inverting a time domain signal to relaxation rate distribution, and dealing with resulting parameters that vary in number, location, and magnitude. Here we invoke well-established machine learning techniques to directly correlate time domain signals to BET surface areas for a set of metal-organic frameworks (MOFs) imbibed with solvent at varied concentrations. We employ this series of MOFs to establish a correlation between NMR signal and surface area via partial least squares (PLS), following screening with principal component analysis, and apply the PLS model to predict surface area of various nanoporous materials. This approach offers a high-throughput, non-destructive way to assess porosity in c.a. one minute. We anticipate this work will contribute to the development of new materials with optimized pore sizes for various applications.

This study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe3+-doped titanium-based metal organic framework (MOF), xFeMIL125-NH2, as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy. For each doping level, time-resolved X-ray transient absorption spectroscopy studies confirm the electron trap site role of the Fe sites in the excited state. Time scan data reveal multiexponential decay kinetics for the charge recombination processes which extend into the microsecond range for all three concentrations. A series of dye photodegradation studies, based on the oxidative decomposition of Rhodamine B, demonstrates the reactivity of the charge separated excited state and the photocatalytic capacity of these MOF materials compared to traditional heterometal-doped semiconductor photocatalysts. [ABSTRACT FROM AUTHOR]

Hydrophobicity has proven fundamental in an inexhaustible amount of everyday applications. Material hydrophobicity is determined by chemical composition and geometrical characteristics of its macroscopic surface. Surface roughness or texturing enhances intrinsic hydrophilic or hydrophobic characteristics of a material. Here we consider crystalline surfaces presenting molecular-scale texturing typical of crystalline porous materials, e.g., metal-organic frameworks. In particular, we investigate one such material with remarkable hydrophobic qualities, ZIF-8. We show that ZIF-8 hydrophobicity is driven not only by its chemical composition but also its sub-nanoscale surface corrugations, a physical enhancement rare amongst hydrophobes. Studying ZIF-8's hydrophobic properties is challenging as experimentally it is difficult to distinguish between the materials' and the macroscopic corrugations' contributions to the hydrophobicity. The computational contact angle determination is also difficult as the standard "geometric" technique of liquid nanodroplet deposition is prone to many artifacts. Here, we characterise ZIF-8 hydrophobicity via: (i) the "geometric" approach and (ii) the "energetic" method, utilising the Young–Dupré formula and computationally determining the liquid–solid adhesion energy. Both approaches reveal nanoscale Wenzel-like bathing of the corrugated surface. Moreover, we illustrate the importance of surface linker termination in ZIF-8 hydrophobicity, which reduces when varied from sp3 N to sp2 N termination. We also consider halogenated analogues of the methyl-imidazole linker, which promote the transition from nanoWenzel-like to nanoCassie–Baxter-like states, further enhancing surface hydrophobicity. Present results reveal the complex interface physics and chemistry between water and complex porous, molecular crystalline surfaces, providing a hint to tune their hydrophobicity. [ABSTRACT FROM AUTHOR]

The liquid-to-vapor transition can occur under unexpected conditions in nanopores, opening the door to fundamental questions and new technologies. The physics of boiling in confinement is progressively introduced, starting from classical nucleation theory, passing through nanoscale effects, and terminating with the material and external parameters that affect the boiling conditions. The relevance of boiling in specific nanoconfined systems is discussed, focusing on heterogeneous lyophobic systems, chromatographic columns, and ion channels. The current level of control of boiling in nanopores enabled by microporous materials such as metal organic frameworks and biological nanopores paves the way to thrilling theoretical challenges and to new technological opportunities in the fields of energy, neuromorphic computing, and sensing. [ABSTRACT FROM AUTHOR]

Gas molecules within Metal-Organic Frameworks (MOFs) have been successfully located for the first time by combining cryo-transferred TEM preparation and cPEDT. This innovative method has solved two known structures and an unreported structure. By precisely locating the positions of gas molecules, host–guest interactions are clarified, advancing our understanding of the adsorption site in the framework materials. [Display omitted] [ABSTRACT FROM AUTHOR]

Atrazine, a human-made herbicide, is infamous for its endocrine-disrupting properties, with adverse consequences on the immune, reproductive, and nervous systems. Consequently, effective recognition of atrazine in various environments, such as water, is critically important. This work presents a precise and efficient method for detecting atrazine across various environments, utilizing a well-established electrochemical technique. A metal organic framework (MOF) ZIF-67 has been synthesized and employed as a catalyst for the electrochemical detection of the triazine herbicide atrazine. Structural, morphological, and chemical analyses were conducted to evaluate the sensing material and to elucidate the interactions between the sensor and the analyte. The ZIF-67 was then integrated on the surface of the working electrode (carbon paste electrode (CPE)) to form a ZIF-67 modified-CPE (ZIF-67/MCPE). The ZIF-67/MCPE was utilized to detect atrazine by electrochemical techniques including differential pulse voltammetry (DPV) and cyclic voltammetry (CV). The sensor demonstrated excellent sensitivity and was effective in detecting atrazine. The modified sensor demonstrated a lower limit of detection (LLOD) of 3.7 μM within a linear concentration range of 4–44 μM and exhibited a strong linear correlation efficiency of 0.97. Computational results corroborated the experimental findings, revealing that the combination of ZIF-67 with atrazine forms minor triangular structures and exhibits enhanced dynamics compared to the pristine MOF. This improvement in the crystallinity of the ZIF-67 MOF with atrazine is attributed to the negative binding energy and reduced energy gap at the interface between the MOF and atrazine. Additionally, the sensor's practical application was evaluated by testing it on sewage water and fresh liquid milk. The sensor demonstrated an exceptional ability to detect atrazine, with a recovery rate ranging from 96% to 99%. This approach holds promise for developing electrochemical or solid-state devices for real-time atrazine monitoring. [ABSTRACT FROM AUTHOR]

The limited conductivity of metal‐organic frameworks (MOFs) poses a significant challenge to their application in the domain of memristors. The proton conduction capabilities of MOFs can be improved through the incorporation of guest molecules. Herein, hydrogen protons are introduced into MIL‐53 (Al) via acid leaching, which not only enhances the proton conductivity of MIL‐53 (Al) but also contributes to its superior resistance switching behavior. The results indicate that untreated MIL‐53 (Al) exhibits negligible resistance switching behavior; however, following hydrochloric acid leaching, it demonstrates excellent retention (103 cycles), longtime durability (103 s), and a favorable ON/OFF ratio (≈25) under bias conditions. Furthermore, under suitable pulse stimulation, the MIL‐53 (Al)‐based memristor successfully emulates biological synaptic behaviors, including excitatory postsynaptic current and paired pulse facilitation. This research presents a novel approach for enhancing the resistive switching performance of MOF‐based memristors. [ABSTRACT FROM AUTHOR]

We present a compelling strategy for fabricating a hierarchical OER electrode, successively consisting of the nickel foam (NF) conductive substrate, carbon-incorporated cobalt oxide nanorod arrays, and nickel-iron hydroxide nanosheets (NF/CoO–C/NiFe–OH). Cobalt-based metal-organic framework (Co-MOF) derived porous CoO–C matrix increases electrical conductivity, facilitates charge transfer, and provides more surface sites for the NiFe–OH deposition. Furthermore, the CoO–C and NiFe–OH heterostructure alters the electronic states of active components, consequently achieving a synergistic role that promotes the OER process. The resulting NF/CoO–C/NiFe–OH exhibits prominent OER activity, with the overpotentials of 281, 347, and 466 mV at 50, 100, and 200 mA cm−2 of current densities, respectively. In the meantime, it also possesses a lower Tafel slope of 39 mV dec−1, larger electrochemical surface area, faster turnover frequencies, and lesser charge transfer resistances. Additionally, the electrode reveals superior stability without significant morphological changes and element valence states. The OER mechanism and electrochemical performance of hierarchical heterostructure regulated by nickel-iron oxyhydroxides on carbon-incorporated cobalt oxide nanorod arrays on the NF substrate (NF/CoO–C/NiFe–OH). [Display omitted] • The in-situ strategy of CoO–C/NiFe–OH hierarchical heterostructure is used. • The CoO–C matrix improves surface structure and electronic states of NiFe–OH. • The NF/CoO–C/NiFe–OH electrode has superior OER performance and durability. • The promoting mechanism of the CoO–C layer on the OER process is proposed. [ABSTRACT FROM AUTHOR]

In this study, Co-bearing Metal-Organic Frameworks (MOFs) are grown via a facile solvothermal process on the surface of two kinds of conductive substrates – titanium dioxide nanotubes (TiO 2 NT) and fluorine-doped tin oxide (FTO) glass and tested as electrodes in the electrochemical hydrogen evolution reaction (HER). The materials derived from three organic linkers - terephthalic acid (Co-BDC), 2-aminoterephthalic acid (Co-BDCNH 2), and trimesic acid (Co-BTC) are characterized by FTIR, Raman, XRD, SEM-EDS, BET, and XPS. Among the layers on FTO without post-synthesis treatment, Co-BTC shows the highest activity (overpotential of HER 1.72 V vs. Ag/AgCl/KCl). The effects of substrate change on TiO 2 NT and annealing of Co-BTC layers in air and argon on their electrocatalytic properties are also studied. Using TiO 2 nanotubes as a substrate and annealing the material in air results in a reduction of the hydrogen evolution overpotential to 1.44 V vs. Ag/AgCl/KCl and a significant reduction in the exchange current density. • Co-based MOFs were successfully fabricated on FTO and TiO 2 NT. • Electrochemical activity depended more on organic linker than substrate type. • Annealing of Co-BTC materials improves catalytic activity in HER. [ABSTRACT FROM AUTHOR]

The rapid development of the electronics market necessitates energy storage devices characterized by high energy density and capacity, alongside the ability to maintain stable and safe operation under harsh conditions, particularly elevated temperatures. In this study, a semi‐solid‐state electrolyte (SSSE) for Li‐metal batteries (LMB) is synthesized by integrating metal–organic frameworks (MOFs) as host materials featuring a hierarchical pore structure. A trace amount of liquid electrolyte (LE) is entrapped within these pores through electrochemical activation. These findings demonstrate that this structure exhibits outstanding properties, including remarkably high thermal stability, an extended electrochemical window (5.25 V vs Li/Li+), and robust lithium‐ion conductivity (2.04 × 10−4 S cm−1), owing to the synergistic effect of the hierarchical MOF pores facilitating the storage and transport of Li ions. The Li//LiFePO4 cell incorporating prepared SSSE shows excellent capacity retention, retaining 97% (162.8 mAh g−1) of their initial capacity after 100 cycles at 1 C rate at an extremely high temperature of 95 °C. It is believed that this study not only advances the understanding of ion transport in MOF‐based SSSE but also significantly contributes to the development of LMB capable of stable and safe operation even under extremely high temperatures. [ABSTRACT FROM AUTHOR]

In a time characterized by the increasing interest in metal–organic frameworks (MOFs) as widely researched crystalline porous substances geared toward enhancing device and system capabilities across diverse environmental contexts, 2D MOFs emerge as a noteworthy class of nanomaterials that integrate the benefits of 2D structures with the unique characteristics inherent to MOFs. These 2D MOFs possess ultrathin nanosheet configuration, abundant accessible active sites, and remarkable mechanical flexibility. Such distinctive properties differentiate them from bulk MOFs and other 2D materials, offering the potential to instigate novel environmental phenomena and applications. This review focuses on the latest progress in the application of 2D MOFs within essential water‐related ecological fields, including contaminant adsorption, photocatalytic degradation, membrane separation, environmental sensing, and disinfection. A variety of synthesis approaches for 2D MOFs are analyzed, accompanied by a discussion on their effectiveness across different environmental settings. The unique structure and features of 2D MOFs that grant outstanding environmental functionalities are compared with those of bulk MOFs. The environmental ramifications of 2D MOFs are highlighted while outlining future research needs to explore the environmental applications of these innovative materials. [ABSTRACT FROM AUTHOR]

Chemistry has traditionally focused on the synthesis of desired compounds, with organic synthesis being a key method for obtaining target molecules. In contrast, self‐assembly —where molecules spontaneously organize into well‐defined structures— has emerged as a powerful tool for fabricating intricate structures. Self‐assembly was initially studied in biological systems but has been developed for synthetic methods, leading to the field of supramolecular chemistry, where non‐covalent interactions/bonds guide molecular assembly. This has led to the development of complex molecular structures, such as metal‐organic frameworks and hydrogen‐bonded organic frameworks. Parallel to this field, cavity quantum electrodynamics (QED), developed in the mid‐20th century, has recently intersected with molecular assembly. Early research in cavity strong coupling focused on inorganic solids and simple molecules, but has since extended to molecular assemblies. The strong coupling synergized with molecular assembly will generate new polaritonic phenomena and applications. [ABSTRACT FROM AUTHOR]

The interface energy level alignment modulation and charge carrier transportation play an important role in the device performance of perovskite solar cells (PSCs). Herein, tailored hydrophobic metal‐organic frameworks (MOFs) are employed as interfacial layers between perovskite absorbers and hole transport layers (HTLs). The tailored MOFs feature abundant carboxylic acid groups capable of bonding with Pb2+ and organic cations, which can effectively passivate interface defects and suppress non‐radiative recombination. Meanwhile, the MOF interfacial layers optimized the energy level alignment between the perovskite and the HTL, further facilitating carrier transportation. Specifically, the CsFAMA‐based PSCs with a bandgap of 1.63 eV attained power conversion efficiency (PCE) of 23.06% upon modification with MOFs. Additionally, the MOFs‐treated FA‐based PSCs with a bandgap of 1.55 eV achieved a remarkable PCE of 24.81%, accompanied by an outstanding fill factor of 84.3% and a minimal open‐circuit voltage loss of merely 0.386 V. Furthermore, the integration of the MOF interfacial layer substantially improved the moisture stability of the PSCs. The unencapsulated CsFAMA PSCs modified with MOFs retained 91.2% of their initial efficiency after 2500 h of aging under ambient conditions with 40% relative humidity (RH). This work underpins the commercialization of PSCs with diverse bandgaps. [ABSTRACT FROM AUTHOR]

ABSTRACT We successfully synthesized a 3D porous lanthanide metal–organic framework, [Tb (obdb)][Tb1/3(H2O)7/3]·NMP (Tb‐MOF) with hydrated terbium ions in the pores by solvothermal method using 4′,4″′‐oxybis[1,1′‐biphenyl]‐3,5‐dicarboxylic acid (H4obdb) as ligand. It is worth mentioning that Tb‐MOF exhibits excellent performance in structural stability and fluorescence response. Even after soaking in various solvents and pH solutions for 3 months, Tb‐MOF can maintain its structural integrity and excellent stability. The fluorescence spectra show that Tb‐MOF not only exhibits the luminescence of the ligand centered at 368 nm (IL), but also emits the characteristic emissions of the metal terbium, among which the luminescence at 542 nm is the strongest. In the detection of antibiotic amphotericin B (AB), Tb‐MOF showed significant detection efficiency. Upon increasing the concentration of AB, the fluorescence intensity at 542 nm gradually decreased, whereas the fluorescence at 368 nm decreased rapidly. The I542/IL value showed a very high linear correlation with AB concentration, with the slope reaching 1.29 × 108 M−1 (0–100 μM). In the field of fluorescent sensors for AB detection, Tb‐MOF is notable not only for its impressively low LOD (limt of detection) of 0.072 nM but also for pioneering the application of a self‐calibrating ratio‐based detection method. To better elucidate this fluorescence sensing phenomenon, we also conducted a detailed discussion of the sensing mechanism for AB. [ABSTRACT FROM AUTHOR]

Non-precious metal catalysts (NPMCs) doped with nitrogen were derived from MOFs. Appropriate ligand and framework order in the precursor ensured the presence of various nitrogenous species and high surface area in the NPC, Ni-NPC, Co-NPC, and Fe-NPC electrocatalysts. Electrochemical properties of the as-prepared electrocatalysts were examined in 0.1 M KOH solution to investigate the effects of metal and doped nitrogen on the oxygen reduction reaction (ORR). The free metal electrocatalyst (NPC) displayed poor ORR activity with an onset potential of 0.87 V RHE. The presence of nickel in the Ni-NPC catalyst could not create more active sites in comparison with the NPC catalyst, while onset potential of the Co-NPC catalyst shifted to 21 mV more positive (Compare to NPC). The investigation of doping active transient metals indicated that Fe-doping could be effective. It was because of the improved ORR activity of the Fe-NPC electrocatalysts with an onset potential of 0.99 V RHE. Furthermore, in a long-term stability test, this optimum electrocatalyst could retain more than 92% of its initial current density and experienced just 57 mV loss in its half-wave potential in an accelerated degradation test. Direct ethanol fuel cell test reveals maximum power density of 19.2 mW cm−2 at ambient temperature. • New M-NPS electrocatalysts were synthesized by pyrolysis of effective MOF precursors. • The synthesized M-N-C electrocatalysts had high surface area and a variety in nitrogenous species. • The effect of the metal on the activity and stability of the M-N-C electrocatalysts was evaluated for ORR. • The sequence of the catalysts activity in ORR are: FeN x > CoN x > NiN x ∼ metal free-N x. [ABSTRACT FROM AUTHOR]

Developing electrode materials with improved catalytic activity is inevitable (i) to achieve efficient electro-catalytic water splitting (EWS) and (ii) to construct high performance dye sensitized solar cells (DSSCs). To this aim, Nitrogen (N)-doped carbon-wrapped bimetallic CoCu alloys (i.e, CN@CoCu) are prepared by directly annealing the Cu-loaded Zeolitic Imidazolate Framework-67 (ZIF-67) metal-organic framework (MOF) and employed as (i) working electrode in EWS and (ii) counter electrode (CE) in DSSCs. The ZIF-67 MOF acts as a self-sacrificing template for the formation of CN@CoCu electrodes, whose electro-catalytic activity can be optimized by tuning the Co/Cu molar ratio (Cu = 0, 5%, 10%, 15% and 20%). The addition of 15% of Cu into the ZIF-67 (i.e., CN@CoCu-15), as the working electrode in water splitting has achieved lowest overpotential values of 91 and 256 mV towards hydrogen evolution reaction and oxygen evolution reaction, respectively. Also, for DSSCs applications, the same CN@CoCu-15 sample as CE displays an improved catalytic activity by 21% higher than that of conventional Pt CE towards tri-iodide redox reaction. Consequently, the CN@CoCu-15 based DSSCs device has achieved a PCE of 7.10% which is larger than that of conventional platinum CE (6.69%). The mechanism behind the improved catalytic activity is attributed to the significant reduction in the work function of CN@CoCu-15 (4.82 eV) compared to CN@Co (5.2 eV), as evidenced from Kelvin Probe Force Microscopic analysis. These findings proposed an efficient bifunctional electro-catalytic material with improved water-splitting performance and solar energy conversion. [Display omitted] • Carbon-wrapped CoCu electrode is prepared for water splitting and DSSC application. • The work function of the electrocatalyst is minimum (4.87) when Co/Cu ratio is 15. • It displays excellent catalytic activity towards KOH and triiodide electrolyte. • Water splitting has been achieved at 1.53 V with prepared CN@CoCu-15. • In DSSC, a PCE of 7.10 % is achieved with prepared CN@CoCu-15 as counter electrode. [ABSTRACT FROM AUTHOR]

Considering the extensive research studies on Ru and Mo2C for the hydrogen evolution reaction (HER), the construction of heterostructure catalysts containing both Ru and Mo2C nanoparticles can further improve the catalytic activity by the synergistic effect of different species. In this work, we report the synthesis of N,P co-doped carbon coated Ru and Mo2C nanoparticles for the HER using a ZnMo metal-organic framework (MOF) as the precursor. The addition of phosphomolybdic acid during the synthesis of a Zn-MOF not only provides a Mo source for the formation of Mo2C, but also induces a nano-bowl structure. After anchoring RuCl3 in the ZnMo-MOF and thermal annealing, Ru and Mo2C nanoparticles encapsulated in N,P doped carbon (Ru-Mo2C@NPC) were synthesized and the nano-bowl morphology was well preserved. Due to the co-existence of the highly active catalytic species Ru and Mo2C, a large specific surface area owing to the evaporation of Zn during the calcination process, and the nano-bowl-like morphology that boosts mass transfer, Ru-Mo2C@NPC exhibits good catalytic activity for the HER over a wide pH range, with overpotentials of 62, 64 and 170 mV in 0.5 M H2SO4, 1 M KOH and 1 M PBS solution at 10 mA cm-2, surpassing the values for many Ru and Mo2C based catalysts. This work provides a feasible route for designing high performance HER catalysts. [ABSTRACT FROM AUTHOR]

A new set of metal-organic frameworks was designed by functionalizing g-C3N4 with benzoic acid and using them as structure-directing ligands during the metal-organic framework (MOF) formation. One such MOF exhibited dual emissions, both metal- and ligand-centered, enabling ratiometric sensing of the carcinogenic industrial solvent dioxane. The fabricated MOFs possessed a unique fluffy spherical morphology that enabled atomic level resolution in transmission electron microscopy--a rarity in MOFs due to the 'Knock-on' effect. Sensor experiments showed a rapid response within 5 s of analyte introduction and achieved a low limit of detection (LOD) of 0.026 ppm, well below the FDA-approved level of 10 ppm. In addition, the sensor exhibited exceptional selectivity, discriminating 1,4-dioxane from a pool of 16 solvents. This increased sensing capability was attributed to the formation of complexes and precise alignment of energy levels between the host and analyte, facilitating photoinduced electron transfer (PET). This material is equally efficient for colorimetric detection of the same solvent under excitation of UV light as well as gas phase detection of this volatile organic compound through I-V characteristics. Density functional theory (DFT) analysis supported the crucial role of Eu and the ligand system in efficiently detecting 1,4-dioxane by fluorescence spectroscopy, as shown in the energy level diagram. Future research could focus on optimizing these metal-organic frameworks for enhanced industrial applications in the detection of dioxane and exploring their potential applications in real-world environmental monitoring and public health safety. [ABSTRACT FROM AUTHOR]

High density, skin effect, and environmental instability are significant limitations that restrict the application of metal-based microwave absorbers in achieving lightweight, high performance, and long service life. This study broke from traditional methods for preparing a microwave absorber Mn 2 O 3 -Fe 3 O 4 @PPy (polypyrrole) by employing an innovative annealing process to convert metal into metal oxide by the introduction of metal organic framework (MOF), which effectively achieving a more lightweight absorber material with hollow porous nanocube structure. Subsequently, PPy was coated onto the metal oxide surface to form a core-shell structure by a situ chemical oxidation synthesis method. The combination of metal oxide of the hollow porous nanocube structure and the core-shell structure formed by highly conductive PPy shell significantly enhanced heterogeneous interfaces and electromagnetic (EM) wave reflection. Excellent dielectric loss and impedance matching contributed evidently to the ultra-wideband EM wave absorption performance. It was demonstrated that, with a filling amount of only 20 wt%, the prepared Mn 2 O 3 -Fe 3 O 4 @PPy achieved an effective bandwidth (EAB) of 10.0 GHz at a thickness of 3.08 mm, with EAB max reaching 13 GHz. At a filling amount of only 10 wt%, the reflection loss (RL) was −62.13 dB, achieving an EAB of 7.4 GHz at 2.98 mm thickness, with EAB max reaching 11.4 GHz. Furthermore, the proposed strategy incorporating metal oxide and PPy enhanced corrosion resistance with higher charge transfer resistance. The ultra-wideband microwave absorption material uses an innovative annealing process for MOF, and then ingenious combines with the coated PPy to form a hollow porous nanocube core-shell structure. Excellent microwave absorption performance: EAB max = 13 GHz, RL min = −62.13 dB, low fill of 10 wt%. In addition, the corrosion resistance of the metal is improved. [Display omitted] [ABSTRACT FROM AUTHOR]

The key issue in utilizing solid polymer electrolytes for high‐energy‐density lithium metal batteries is to balance the conflicting demands of superior processability, adequate ionic conductivity, and mechanical stability. Inspired by molecular structure design, a metal‐organic framework‐derived polyether poly(urethane urea) solid polymer electrolyte (denoted as ePU@H SPE) has been synthesized via a facile polycondensation method involving covalent crosslinking. The reduced crystallinity and numerous polar groups in ePU@H SPEs enhance Li salt dissociation and create efficient Li+ ion diffusion channels, yielding remarkable ionic conductivity (1.48 × 10−4 S cm−1). The polymer backbones, incorporating covalent bonds and dynamic hydrogen bonds, provide superb mechanical strength (5.12 GPa), high toughness (1240%), and excellent resilience, which suppress lithium dendrite growth and buffer electrode volume fluctuations during cycling. Leveraging these attributes, the well‐designed ePU@H SPE enables ultra‐high durability in lithium plating/stripping over 2300 h. Moreover, the integrated LFP|ePU@H|Li batteries, generating delicate electrode/electrolyte interfacial contact, deliver an exceptionally long lifespan (86% retention over 500 cycles at 1 C). Moreover, the LFP|ePU@H|Li pouch cell operates reliably even under severe deformation and external damage. Impressively, the stable cycling performance of full batteries incorporating high‐voltage LCO and high‐capacity S cathodes further verifies the significant potential of advanced ePU@H SPEs for practical applications. [ABSTRACT FROM AUTHOR]

Hygroscopic metal–organic frameworks (MOFs) are considered as superior moisture sorbents due to their highly adjustable and desired water adsorption/release performance, enabling effective atmospheric water harvesting (AWH) in arid regions. However, the water adsorption capacity, recycling stability, and functionality of current MOFs should be further improved to meet the requirements of practical AWH systems. Here the hydrophilicity at low relative humidity (RH) and cycling stability of MOF‐808 are simultaneously enhanced through the ethylenediaminetetraacetic acid (EDTA)‐mediated post‐modification. Based on the structural reinforcement, EDTA‐modified MOF‐808 (E‐MOF‐808) delivers a stable water uptake capacity of 0.39 g g−1 at 25% RH even after 50 water adsorption–desorption cycles, more than five times that of pristine MOF‐808. In addition, bridging by EDTA with the strong chelating ability, the E‐MOF‐808 can spontaneously capture Cu2+ for further functional improvement. Accordingly, light‐absorbing CuS nanoparticles can be in situ decorated on E‐MOF‐808 for facilitating solar‐driven water release. It is envisioned that this EDTA‐mediated function enhancement should provide valuable insights into the all‐in‐one design of versatile MOFs sorbents. [ABSTRACT FROM AUTHOR]

Efficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag27TPyP‐Fe. With water as electron donors, Ag27TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g−1 h−1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g−1 h−1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high‐purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity. [ABSTRACT FROM AUTHOR]

Efficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag27TPyP‐Fe. With water as electron donors, Ag27TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g−1 h−1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g−1 h−1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high‐purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity. [ABSTRACT FROM AUTHOR]

The unique catalytic properties of natural enzymes have inspired chemists to develop biomimetic catalyst platforms for the intention of retaining the unique functions and solving the application limitations of enzymes, such as high costs, instability and unrecyclable ability. Porous materials possess unique advantages for the construction of biomimetic catalysts, such as high surface areas, thermal stability, permanent porosity and tunability. These characteristics make them ideal porous matrices for the construction of biomimetic catalysts by immobilizing enzyme-mimic active sites inside porous materials. The developed porous biomimetic catalysts demonstrate high activity, selectivity and stability. In this feature article, we categorize and discuss the recently developed strategies for introducing enzyme-mimic active species inside porous materials, which are based on the type of employed porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), molecular sieves, porous metal silicate (PMS) materials and porous carbon materials. The advantages and limitations of these porous materials-based biomimetic catalysts are discussed, and the challenges and future directions in this field are also highlighted. [ABSTRACT FROM AUTHOR]

Reticular chemistry has In the post-synthetic modification (PSM) of frameworks one of the most versatile tools to adapt the systems' physicochemical properties to the specific requirements which are imposed by their application in different contexts. We can safely say that PSM methodologies in all their variants are currently one of the main resources that reticular chemists turn to when they need to diversify a framework compositionally. Practically all these modifications require the integration of functional groups appended to the organic linkers in the framework, either by direct synthesis or by post-synthetic exchange. The reactivity of these tags allows, at a subsequent stage, covalent modification of the framework under conditions that ideally respect its structural integrity. In this perspective article we introduce the use of tetrazine-based linkers as intrinsically tagged alternatives to integrate PSM with click chemistry reactivity. This strategy is ideally suited to molecular frameworks, as it combines very mild modification conditions with direct control over the organisation of built-in appendices and the acknowledged potential of click chemistry to build framework libraries. [ABSTRACT FROM AUTHOR]

Efficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag27TPyP‐Fe. With water as electron donors, Ag27TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g−1 h−1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g−1 h−1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high‐purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity. [ABSTRACT FROM AUTHOR]

Efficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag27TPyP‐Fe. With water as electron donors, Ag27TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g−1 h−1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g−1 h−1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high‐purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity. [ABSTRACT FROM AUTHOR]

The increasing prevalence of multidrug-resistant pathogens is a critical public health issue, necessitating the development of alternative antibacterial agents. Examples of these pathogens are methicillin-resistant Staphylococcus aureus (MRSA) and the emergence of "pan-resistant" Gram-negative strains, such as Pseudomonas aeruginosa and Acinetobacter baumannii, which occurred more recently. This review examines various emerging materials with significant antibacterial activities. Among these are nanomaterials such as quantum dots, carbon quantum dots, metal–organic frameworks (MOFs), covalent organic frameworks (COFs), and layered double hydroxides, all of which demonstrate excellent antibacterial properties. Interestingly, including antibacterial agents within the structure of these materials can help avoid bacterial resistance and improve the long-term efficacy of the materials. Additionally, the antibacterial potential of liquid solvents, including ionic liquids and both deep eutectic solvents and natural deep eutectic solvents, is explored. The review discusses the synthesis methods, advantages, and antibacterial efficacy of these new materials. By providing a comprehensive overview of these innovative materials, this review aims to contribute to the ongoing search for effective solutions to combat antibiotic resistance. Key studies demonstrating antibacterial effects against pathogens like Escherichia coli, Staphylococcus aureus, and multidrug-resistant strains are summarized. MOFs have exhibited antibacterial properties through controlled ion release and surface interactions. COFs have enhanced the efficacy of encapsulated antibiotics and displayed intrinsic antibacterial activity. Other nanomaterials, such as quantum dots, have generated reactive oxygen species, leading to microbial inactivation. This review aims to provide insights into these new classes of antibacterial materials and highlight them for addressing the global crisis of antibiotic resistance. Key points: • Nanomaterials show strong antibacterial effects against drug-resistant bacteria • Emerging solvents like ionic liquids offer novel solutions for bacterial resistance • MOFs and COFs enhance antibiotic efficacy, showing promise in combating resistance [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Electrocatalytic reduction of CO2 to valuable products possesses huge potential to alleviate environmental and energy crisis. It is well known that Ag favors the conversion of CO2 to CO but the exposed active sites and stability are still rather limited. In this study, a novel one‐dimensional Ag‐based metal‐organic framework (1D Ag‐NIM‐MOF) was successfully synthesized and used in the electrocatalytic CO2 reduction reaction (CO2RR) for the first time. As a result, the Faradaic efficiency of CO achieved 94.5% with current density of 12.5 mA·cm–2 in an H‐type cell and 98.2% with current density of 161 mA·cm–2 in a flow cell at –1.0 V (vs. RHE), which stands as a new benchmark of Ag‐based MOFs in the electrocatalytic CO2RR. The excellent performance of 1D Ag‐NIM‐MOF is attributed to its peculiar one‐dimensional structure, which is beneficial for diffusion of reactants and products, and exposure of much more catalytic sites. Compared to commercial Ag nanoparticles, 1D Ag‐NIM‐MOF exhibits superior electrocatalytic CO2RR performance with higher catalytic activity and stability. [ABSTRACT FROM AUTHOR]

The quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach is widely used in sample pretreatment in agricultural products, food, environment, etc. And nano-materials are widely used in QuEChERS method due to its small size and large specific surface area. In this review, we examine the typical applications of several commonly used nano-materials in improved QuEChERS method. These materials include multi-walled carbon nanotubes (MWCNTs) and their derivatives, magnetic nanoparticles (MNPs), metal organic frameworks (MOFs), covalent organic frameworks (COFs), graphene oxide (GO), lipid and protein adsorbent (LPAS), cucurbituril (CBs), and carbon nano-cages (CNCs), and so on. The strengths and weaknesses of each nano-material are presented, as well as the challenging aspects that need to be addressed in future research. By comparing the applications and the current technology development, this review suggests utilizing artificial intelligence (AI) to screen suitable combinations of purification agents and performing virtual simulation experiments to verify the reliability of this methodology. By doing so, we aim to accelerate the development of new products and decrease the cost of innovation. It also recommends designing smarter pretreatment instruments to enhance the convenience and automation of the sample pretreatment process and reduce the margin for human error. [ABSTRACT FROM AUTHOR]

A novel acyl chloride-mediated strategy is used to synthesize rhodanine-modified UiO-66 adsorbent. Benefitting from the high grafting density of rhodanine, the optimal UiO-66-NH 2 @20Rd exhibits ultra-high adsorption capacity and selectivity for Ag(I) recovery. This study highlights that such a general strategy can provide a valuable avenue toward various functional adsorption materials. [Display omitted] Silver (Ag) recovery is essential for ecological protection, human health and economic benefits. Effective capture of Ag(I) from wastewater is still challenging due to insufficient accessible sites of adsorbents. Herein, an acyl chloride-mediated strategy is developed to synthesize rhodanine (Rd) modified UiO-66 derivatives for Ag(I) adsorption. Benefitting from the high grafting density of Rd, the optimal Rd-modified UiO-66-NH 2 (UiO-66-NH 2 @20Rd) features an ultra-high uptake capacity (maximum capacity of 923.9 mg·g−1) and selectivity (maximum selectivity coefficient of 1665.52) for Ag(I). Almost 90 % of Ag(I) could be captured in one minute over UiO-66-NH 2 @20Rd and maintained a removal rate of 98.9 % even after six cycles. Moreover, a fixed-bed column test demonstrates that approximately 21,780 bed volumes of Ag(I) simulated wastewater can be effectively treated, indicating great promise for practical application. Mechanism investigation illustrates that outstanding performance can be attributed to the synergistic effect of Ag(I) adsorption and reduction on dense rhodanine sites. This study highlights that such a general strategy can provide a valuable avenue toward various functional adsorption materials. [ABSTRACT FROM AUTHOR]

The pyrazine-based Fe-MOFs with modulated O-Fe-N coordination were developed by ligand substitution strategy, which exhibited enhanced catalytic hydroxyl radical (OH) generation in Fenton-like process via degreasing H 2 O 2 activation barrier and triggering OH involved Fe(III) reduction. [Display omitted] Rational design of coordination environment of Fe-based metal-organic frameworks (Fe-MOFs) is still a challenge in achieving enhanced catalytic activity for Fenten-like advanced oxidation process. Here in, novel porous Fe-MOFs with modulated O-Fe-N coordination was developed by configurating amino terephthalic acid (H 2 ATA) and pyrazine-dicarboxylic acid (PzDC) (Fe-ATA/PzDC-7:3). PzDC ligands introduce pyridine-N sites to form O-Fe-N coordination with lower binding energy, which affect the local electronic environment of Fe-clusters in Fe-ATA, thus decreased its interfacial H 2 O 2 activation barrier. O-Fe-N coordination also accelerate Fe(II)/Fe(III) cycling of Fe-clusters by triggering the reactive oxidant species mediated Fe(III) reduction. As such, Fe-ATA/PzDC-7:3/H 2 O 2 system exhibited excellent degradation performance for typical antibiotic sulfamethoxazole (SMX), in which the steady-state concentration of hydroxyl radical (OH) was 1.6 times higher than that of unregulated Fe-ATA. Overall, this study highlights the role of O-Fe-N coordination and the electronic environment of Fe-clusters on regulating Fenton-like catalytic performance, and provides a platform for precise engineering of Fe-MOFs. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel and simple scheme for loading aluminum hypophosphite on MOF derivatives. • The dual function of carboxymethyl cellulose: buffer and support layer. • The double-layer hollow nano hybrid is integrated with multiple flame retardant elements. • The flame retardancy of epoxy resin composites is significantly improved after the introduction of AHP/ACP@CMC due to its unique components and nanostructure. Aluminum hypophosphite (AHP) has been used as a flame retardant for a long time. Previous studies about AHP employed in flame retardant materials mostly focus on coating, modification, and complex system. It is valuable to explore simple experimental steps to prepare nano hybrids with AHP and metal–organic frameworks (MOFs). We found acidic substances could etch zeolitic imidazolate framework-67 (ZIF-67) to obtain MOF derivatives. Unfortunately, AHP and ZIF-67 could not directly form a hybrid. Therefore, carboxymethylcellulose (CMC) is introduced as a dual function layer (buffer and support). The CMC resists the complete conversion of ZIF-67 etched by phosphoric acid to amorphous cobalt phosphate hydrate (ACP). Meanwhile, CMC containing hydroxyl groups combines with AHP through electrostatic interaction and coordination bonds. A double-layer hollow MOF derivative is synthesized through this one-stone-two-birds strategy. Due to multiple flame retardant elements and unique nanostructure, this MOF derivative endows epoxy (EP) resin with excellent flame retardancy. With 2.0 wt% addition, the peak heat release rate (pHRR) and total heat release (THR) of EP/AHP/ACP@CMC are decreased by 47.8 and 21.0 %, respectively. This study proposes a novel scheme that converts AHP into MOF derivatives as high-performance FRs. [ABSTRACT FROM AUTHOR]