Self-Assembled Carbon Metal-Organic Framework Oxides Derived from Two Calcination Temperatures as Anode Material for Lithium-Ion Batteries.

Owing to their structural diversity and mesoporous construction, metal-organic frameworks (MOFs) have been used as templates to prepare mesoporous metal oxides, which show excellent performance as anode materials for lithium-ion batteries (LIBs). Co-ZnO/C and Co-Co3O4/C nanohybrids were successfully synthesized based on a precursor of Co-doped MOF-5 by accurately controlling the annealing temperature and atmosphere. Experimental data proved that their electrochemical performance was closely associated with the material phase, especially for Co-ZnO/C, indicating that carbon skeleton materials can maintain a good restoration rate of over 99% after undergoing high-current density cycling. Meanwhile, Co-Co3O4/C nanohybrids showed an exceedingly high reversible capacity of 898 mAh∙g-1 at a current density of 0.1 C after 100 cycles. Their improved coulombic efficiency and superior rate capability contribute to a mesoporous structure, which provides pathways allowing for rapid Li+ diffusion and regulates volume change during charge and discharge processes.

Signal-On Detection of Caspase-3 with Methylene Blue-Loaded Metal-Organic Frameworks as Signal Reporters.

In this work, we report on an electrochemical method for the signal-on detection of caspase-3 and the evaluation of apoptosis based on the biotinylation reaction and the signal amplification of methylene blue (MB)-loaded metal-organic frameworks (MOFs). Zr-based UiO-66-NH2 MOFs were used as the nanocarriers to load electroactive MB molecules. Recombinant hexahistidine (His6)-tagged streptavidin (rSA) was attached to the MOFs through the coordination interaction between the His6 tag in rSA and the metal ions on the surface of the MOFs. The acetylated peptide substrate Ac-GDEVDGGGPPPPC was immobilized on the gold electrode. In the presence of caspase-3, the peptide was specifically cleaved, leading to the release of the Ac-GDEVD sequence. A N-terminal amine group was generated and then biotinylated in the presence of biotin-NHS. Based on the strong interaction between rSA and biotin, rSA@MOF@MB was captured by the biotinylated peptide-modified electrode, producing a significantly amplified electrochemical signal. Caspase-3 was sensitively determined with a linear range from 0.1 to 25 pg/mL and a limit of detection down to 0.04 pg/mL. Further, the active caspase-3 in apoptosis inducer-treated HeLa cells was further quantified by this method. The proposed signal-on biosensor is compatible with the complex biological samples and shows great potential for apoptosis-related diagnosis and the screening of caspase-targeting drugs.

Investigation of the Sensing Properties of Lanthanoid Metal-Organic Frameworks (Ln-MOFs) with Terephthalic Acid.

The solvothermal synthesis of LnCl3.nH2O with terephthalic acid (benzene-1,4-dicarboxylic acid, H2BDC) produced metal-organic frameworks (LnBDC), [Ln2(BDC)3(H2O)4]∞, where Ln = Sm, Eu, Tb, and Dy. The materials obtained were characterized by a number of physico-chemical techniques. The influence of the ionic radius of the lanthanides on the microstructural characteristics of the Ln-MOFs was evaluated by performing Rietveld refinement. The MOFs obtained were tested as fluorescent sensors for numerous cations and anions in water. The highly luminescent EuBDC and TbBDC demonstrated multi-responsive luminescence sensing functions to detect Ag(I), Fe(III), Cr(III), and Cr(VI), which are essential for their environmental applications. By applying the non-linear Stern-Volmer equation, the fluorescent quenching mechanism was determined. The stability of the obtained materials in water in a wide pH range (acidity pH = 4 and alkalinity pH = 9 solutions) was confirmed.

Isoreticular Metal-Organic Framework-3 (IRMOF-3): From Experimental Preparation, Functionalized Modification to Practical Applications.

Isoreticular metal-organic framework-3 (IRMOF-3), a porous coordination polymer, is an MOF material with the characteristics of a large specific surface area and adjustable pore size. Due to the existence of the active amino group (-NH2) on the organic ligand, IRMOF-3 has more extensive research and application potential. Herein, the main preparation methods of IRMOF-3 in existing research were compared and discussed first. Second, we classified and summarized the functionalization modification of IRMOF-3 based on different reaction mechanisms. In addition, the expanded research and progress of IRMOF-3 and their derivatives in catalysis, hydrogen storage, material adsorption and separation, carrier materials, and fluorescence detection were discussed from an application perspective. Moreover, the industrialization prospect of IRMOF-3 and the pressing problems in its practical application were analyzed and prospected. This review is expected to provide a reference for the design and application of more new nanomaterials based on IRMOF-3 to develop more advanced functional materials in industrial production and engineering applications.

Recent development of metal-organic frameworks and their composites in electromagnetic wave absorption and shielding applications.

With the rapid development of information and communication industries, the usage of electromagnetic waves has caused the hazard of human health and misfunction of devices. The adsorption and shielding of electromagnetic waves have been achieved in various materials. The unique adjustable spatial structure makes metal-organic frameworks (MOFs) promising for electromagnetic shielding and adsorbing. As MOFs research advances, various large-scale MOF-based materials have been developed. For instance, MOFs spatial structure has been expanded from 2D to 3D to load more ligands. Progress in synthetic methods for MOFs and their derivatives is advancing, with priority on large-scale preparation and green synthesis. This review summarizes the methods for synthesizing MOFs and their derivatives, and explores the effects of MOFs spatial structure on electromagnetic interference (EMI) shielding and electromagnetic wave absorption capabilities. At the same time, detailed examples are used to focus on the applications of five different MOFs composites in electromagnetic shielding and electromagnetic wave absorption. Finally, the current challenges and prospects of MOFs in the electromagnetic field are introduced, providing a useful reference for the preparation and design of MOFs and their composites for electromagnetic wave processing applications.

Toward understanding ammonia capture in two amino-functionalized metal-organic frameworks using in-situ infrared spectroscopy and DFT calculation.

Two isostructural, three-dimensional, interpenetrated amino-functionalized Metal-Organic Frameworks (Co-2AIN-MOF and Cd-2AIN-MOF) based on 2-aminoisonicotinic acid (2AIN) were synthesized, structurally characterized and determined. Based on the PXRD analysis, the solvent exchange hardly changed their framework structure, and the samples fully activated by methanol can be achieved and examined by infrared spectroscopy. Due to the presence of the carbonyl group and free amino groups in the pore of the framework, the NH3 uptakes of Co-2AIN-MOF and Cd-2AIN-MOF are 11.70 and 13.81 mmol/g and at 1 bar, respectively. In-situ Infrared spectroscopy and DFT calculations revealed the different adsorption sites and processes between Co-2AIN-MOF and Cd-2AIN-MOF.

Phototactic/Photosynthetic/Magnetic-Powered Chlamydomonas Reinhardtii-Metal-Organic Frameworks Micro/Nanomotors for Intelligent Thrombolytic Management and Ischemia Alleviation.

Thrombosis presents a critical health threat globally, with high mortality and incidence rates. Clinical treatment faces challenges such as low thrombolytic agent bioavailability, thrombosis recurrence, ischemic hypoxia damage, and neural degeneration. This study developed biocompatible Chlamydomonas Reinhardtii micromotors (CHL) with photo/magnetic capabilities to address these needs. These CHL micromotors, equipped with phototaxis and photosynthesis abilities, offer promising solutions. A core aspect of this innovation involves incorporating polysaccharides (glycol chitosan (GCS) and fucoidan (F)) into ferric Metal-organic frameworks (MOFs), loaded with urokinase (UK), and subsequently self-assembled onto the multimodal CHL, forming a core-shell microstructure (CHL@GCS/F-UK-MOF). Under light-navigation, CHL@GCS/F-UK-MOF is shown to penetrate thrombi, enhancing thrombolytic biodistribution. Combining CHL@GCS/F-UK-MOF with the magnetic hyperthermia technique achieves stimuli-responsive multiple-release, accelerating thrombolysis and rapidly restoring blocked blood vessels. Moreover, this approach attenuates thrombi-induced ischemic hypoxia disorder and tissue damage. The photosynthetic and magnetotherapeutic properties of CHL@GCS/F-UK-MOF, along with their protective effects, including reduced apoptosis, enhanced behavioral function, induced Heat Shock Protein (HSP), polarized M2 macrophages, and mitigated hypoxia, are confirmed through biochemical, microscopic, and behavioral assessments. This multifunctional biomimetic platform, integrating photo-magnetic techniques, offers a comprehensive approach to cardiovascular management, advancing related technologies.

In-situ activation of biomimetic single-site bioorthogonal nanozyme for tumor-specific combination therapy.

Copper-catalyzed click chemistry offers creative strategies for activation of therapeutics without disrupting biological processes. Despite tremendous efforts, current copper catalysts face fundamental challenges in achieving high efficiency, atom economy, and tissue-specific selectivity. Herein, we develop a facile "mix-and-match synthetic strategy" to fabricate a biomimetic single-site copper-bipyridine-based cerium metal-organic framework (Cu/Ce-MOF@M) for efficient and tumor cell-specific bioorthogonal catalysis. This elegant methodology achieves isolated single-Cu-site within the MOF architecture, resulting in exceptionally high catalytic performance. Cu/Ce-MOF@M favors a 32.1-fold higher catalytic activity than the widely used MOF-supported copper nanoparticles at single-particle level, as first evidenced by single-molecule fluorescence microscopy. Furthermore, with cancer cell-membrane camouflage, Cu/Ce-MOF@M demonstrates preferential tropism for its parent cells. Simultaneously, the single-site CuII species within Cu/Ce-MOF@M are reduced by upregulated glutathione in cancerous cells to CuI for catalyzing the click reaction, enabling homotypic cancer cell-activated in situ drug synthesis. Additionally, Cu/Ce-MOF@M exhibits oxidase and peroxidase mimicking activities, further enhancing catalytic cancer therapy. This study guides the reasonable design of highly active heterogeneous transition-metal catalysts for targeted bioorthogonal reactions.

Low-potential anodic electrochemiluminescence of terbium metal-organic frameworks for selective microRNA-155 detection.

High excitation potential is recognized as a harmful factor for the biological activity of biomacromolecules, such as proteins and nucleic acids, in electrochemiluminescence (ECL) biosensing. Developing low-potential ECL luminophores is vital for improving ECL accuracy in actual sample sensing. In this work, based on porous metal-organic framework (MOF) structure with multiple active sites and energy transfer between the excited ligands and Ln nodes, we designed a series of Ln-MOFs and observed ECL emission at low potential, providing a novel method to realize low-potential ECL. The MOF nanoemitters were prepared using 1,3,5-tri (4-carboxyphenyl)benzene ligand and several lanthanide ions as nodes through mild hydrothermal reaction. Interestingly, strong ECL emission at +0.75 V of peak potential was observed in the ECL-potential curve of Tb-based MOF using 2,2',2″-nitrilotriethanol as coreactant, which was beneficial for reducing background interference in biosensing, and this ECL emission was attributed to the energy transfer between Tb and excited ligand. This low-potential ECL was then applied to construct an ECL biosensor with newly developed Cas12a-based method for selective detection of microRNA-155 without the help of strand displacement or reverse transcription. For this ECL system, the limit of detection was 0.78 nM, and the overall detection time was 2.5 h. The Ln-MOF nanoemitter provides a robust ECL platform to selectively detect various targets by integrating new bio-related techniques.

Surface engineering of metal-organic framework nanoparticles-based miRNA carrier: Boosting RNA stability, intracellular delivery and synergistic therapy.

MicroRNAs (miRNAs) are small noncoding RNAs that are critical for the regulation of multiple physiological and pathological processes, thus holding great clinical potential. However, the therapeutic applications of miRNAs are severely limited by their biological instability and poor intracellular delivery. Herein, we describe a dual-layers surface engineering strategy to design an efficient miRNA delivery nanosystem based on metal-organic frameworks (MOFs) incorporating lipid coating. The resulting nanoparticle system was demonstrated to protect miRNA from ribonuclease degradation, enhance cellular uptake and facilitate lysosomal escape. These ensured effective miRNA mediated gene therapy, which synergized with MOF-specific photodynamic therapy and pre-encapsulated doxorubicin (Dox) chemotherapy to provide a multifunctional with therapeutic effectiveness against cencer cells The mechanisms of miRNA binding and Dox loading were revealed, demonstrating the potential of the present MOFs surface-engineered strategy to overcome their inherent pore-size restriction for macromolecular miRNA carrying, enableefficient co-delivery. In vitro studies revealed the potential of our multifunctional system for miRNA delivery and the demonstrated the therapeutic effectiveness against cancer cells, thereby providing a versatile all-in-one MOFs strategy for delivery of nucleic acids and diverse therapeutic molecules in synergistic therapy.

Linking mechanochemistry with the green chemistry principles: Review article.

The need to explore contemporary alternatives for industrial production has driven the development of innovative techniques that address critical limitations linked to traditional batch mechanochemistry. One particularly promising strategy involves the integration of flow processes with mechanochemistry. Three noteworthy technologies in this domain are single-screw extrusion (SSE) and twin-screw extrusion (TSE) and Impact (Induction) in Continuous-flow Heated Mechanochemistry (ICHeM). These technologies go beyond the industrial production of polymers, extending to the synthesis of active pharmaceutical ingredients, the fabrication of (nano)materials, and the extraction of high-added value products through the valorisation of biomass and waste materials. In accordance with the principles of green chemistry, ball milling processes are generally considered greener compared to conventional solvothermal processes. In fact, ball milling processes require less solvent, enhance reaction rates and reaction conversion by increasing surface area and substituting thermal energy with mechanochemical energy, among others. Special attention will be given to the types of products, reactants, size of the milling balls and reaction conditions, selecting 60 articles after applying a screening methodology during the period 2020-2022. This paper aims to compile and analyze the cutting edge of research in utilizing mechanochemistry for green chemistry applications.

A Computation-guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-dimensional Conductive Metal-organic Framework for Efficient H2O2 Electrosynthesis.

Electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e--ORR) provides an alternative method to the energy-intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e--ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e--ORR-inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first-principle predictions, a substrate-free and two-dimensional conductive metal-organic framework (Ni-TCPP(Co)), composed of Co-N4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi-site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni-TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high-density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni-TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e--ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90%/85% H2O2 selectivity within 0-0.8 V vs. RHE and >18.2/18.0 mol g-1 h-1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high-density active sites, promoting high-efficiency electrosynthesis of H2O2 and beyond.

Modification of metals and ligands in two-dimensional conjugated metal-organic frameworks for CO2 electroreduction: A combined density functional theory and machine learning study.

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technology to establish an artificial carbon cycle. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with high electrical conductivity have great potential as catalysts. Herein, we designed a range of 2D c-MOFs with different transition metal atoms and organic ligands, TMNxO4-x-HDQ (TM = Cr∼Cu, Mo, Ru∼Ag, W∼Au; x  = 0, 2, 4; HDQ = hexadipyrazinoquinoxaline), and systematically studied their catalytic performance using density functional theory (DFT). Calculation results indicated that all of TMNxO4-x-HDQ structures possess good thermodynamic and electrochemical stability. Notably, among the examined 37 MOFs, 6 catalysts outperformed the Cu(211) surface in terms of catalytic activity and product selectivity. Specifically, NiN4-HDQ emerged as an exceptional electrocatalyst for CO production in CO2RR, yielding a remarkable low limiting potential (UL) of -0.04 V. CuN4-HDQ, NiN2O2-HDQ, and PtN2O2-HDQ also exhibited high activity for HCOOH production, with UL values of -0.27, -0.29, and -0.27 V, respectively, while MnN4-HDQ, and NiO4-HDQ mainly produced CH4 with UL values of -0.58 and -0.24 V, respectively. Furthermore, these 6 catalysts efficiently suppressed the competitive hydrogen evolution reaction. Machine learning (ML) analysis revealed that the key intrinsic factors influencing CO2RR performance of these 2D c-MOFs include electron affinity (EA), electronegativity (χ), the first ionization energy (Ie), p-band center of the coordinated N/O atom (εp), the radius of metal atom (r), and d-band center (εd). Our findings may provide valuable insights for the exploration of highly active and selective CO2RR electrocatalysts.

A new UiO-66-NH2 MOF-based nano-immobilized DFR enzyme as a biocatalyst for the synthesis of anthocyanidins.

Anthocyanidins and anthocyanins are one subclass of flavonoids in plants with diverse biological functions and have health-promoting effects. Dihydroflavonol 4-reductase (DFR) is one of the important enzymes involved in the biosynthesis of anthocyanidins and other flavonoids. Here, a new MOF-based nano-immobilized DFR enzyme acting as a nano-biocatalyst for the production of anthocyanidins in vitro was designed. We prepared UiO-66-NH2 MOF nano-carrier and recombinant DFR enzyme from genetic engineering. DFR@UiO-66-NH2 nano-immobilized enzyme was constructed based on covalent bonding under the optimum immobilization conditions of the enzyme/carrier ratio of 250 mg/g, 37 °C, pH 6.5 and fixation time of 10 min. DFR@UiO-66-NH2 was characterized and its catalytic function for the synthesis of anthocyanidins in vitro was testified using UPLC-QQQ-MS analysis. Compared with free DFR enzyme, the enzymatic reaction catalyzed by DFR@UiO-66-NH2 was more easily for manipulation in a wide range of reaction temperatures and pH values. DFR@UiO-66-NH2 had better thermal stability, enhanced adaptability, longer-term storage, outstanding tolerances to the influences of several organic reagents and Zn2+, Cu2+ and Fe2+ ions, and relatively good reusability. This work developed a new MOF-based nano-immobilized biocatalyst that had a good prospect of application in the green synthesis of anthocyanins in the future.

Selective detection of food contaminants using engineered gallium-organic frameworks with MD and metadynamics simulations.

The exclusion mechanism of food contaminants such as bisphenol A (BPA), Flavonoids (FLA), and Goitrin (GOI) onto the novel gallium-metal organic framework (MOF) and functionalized MOF with oxalamide group (MOF-OX) is evaluated by utilizing molecular dynamics (MD) and Metadynamics simulations. The atoms in molecules (AIM) analysis detected different types of atomic interactions between contaminant molecules and substrates. To assess this procedure, a range of descriptors including interaction energies, root mean square displacement, radial distribution function (RDF), density, hydrogen bond count (HB), and contact numbers are examined across the simulation trajectories. The most important elements in the stability of the systems under examination are found to be stacking π-π and HB interactions. It was confirmed by a significant value of total interaction energy for BPA/MOF-OX (- 338.21 kJ mol-1) and BPA/MOF (- 389.95 kJ mol-1) complexes. Evaluation of interaction energies reveals that L-J interaction plays an essential role in the adsorption of food contaminants on the substrates. The free energy values for the stability systems of BPA/MOF and BPA/MOF-OX complexes at their global minima reached about BPA/MOF = - 254.29 kJ mol-1 and BPA/MOF-OX = - 187.62 kJ mol-1, respectively. Nevertheless, this work provides a new strategy for the preparation of a new hierarchical tree-dimensional of the Ga-MOF hybrid material for the adsorption and exclusion of food contaminates and their effect on human health.

Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States.

The first wide-view image of multiple structural and phase transformations for MOFs from crystal state transformations further to the extreme limit approaching liquid/glass phase, was presented based on a square-layer framework of [Co2(pybz)2(CH3COO)2]·DMF (Co2). The process involves i) an initial crystalline transformation brings to a 3-fold interpenetrated and ordered vacancies contained framework [Co(pybz)2(CH3OH)2]·2CH3OH (CoM) due to in-situ disassemble-reassemble, ii) thermal induced departure of a pair of cis-form coordinated methanol in CoM leads to amorphous framework (a-dCoM), iii) glass transition (Tg = 566 K) to super-cooled liquid (scl-dCoM, spanning 38 K), iv) obtaining MOF glass g-dCoM upon quenching the super-cooled liquid, and v) re-crystallization of super-cooled liquid to six-fold interpenetrated dia-net framework [Co(pybz)2]6n (rec-dCoM) under heating above 604 K. The access to glass from CoM, provides a new self-perturbation strategy to create more MOF glasses without melting. The wider pore size distribution in amorphous/glassy MOFs than crystalline precursor realized the first time selective hydrocarbon gas separation by breakthrough experiments, which bring efficient separation of 1:99 C2H2/C2H4 by either a-dCoM or g-dCoM and produce polymer grade C2H4 with purity ≥ 99.5% after a single adsorption process. Furthermore, the mixture of 50:50 C3H6/C3H8 can be separated by a-dCoM.

Self-Supporting Hierarchical Carbon Network Loaded with NiW Nanoparticles for Efficient Hydrogen Evolution.

Water splitting technology can convert renewable energies such as solar and wind into hydrogen energy, which is key to achieving a low-carbon hydrogen economy cycle. However, Pt-based catalysts for hydrogen evolution reaction (HER) are too expensive, thus it needs to develop efficient non-noble metal catalysts as alternatives. Herein, Ni-BDC-loaded carbon cloth (CC) is co-pyrolyzed with urea to obtain a composite structure of carbon nanotubes (CNT) and porous carbon (PC) embedded with W-doped Ni nanoparticles on CC, resulting in NiW-CNT/PC/CC. Benefiting from the synergistic effect between Ni and W, the high conductivity of CNT, and the high mass transfer rate of PC, NiW-CNT/PC/CC exhibits excellent HER activity in KOH, which only requires a low overpotential of 45 mV to drive a current density of 10 mA cm-2 with stability exceeding 40 h. Simulation calculations confirm that the W doping in metal Ni can optimize its electronic structure by lowering the d-band center and weakening hydrogen adsorption, thus reducing its HER barrier.

Symmetry-Breaking and Symmetry-Retaining Morphological Evolution of the Single Crystals of Cyclodextrin Metal-Organic Frameworks.

The morphological symmetry-retaining and symmetry-breaking of single crystals of the γ-cyclodextrin metal-organic framework have been achieved via introducing lower symmetric ß-cyclodextrins and α-cyclodextrins, respectively. ß-cyclodextrins led to a morphological evolution with retained symmetry from cubic to rhombic dodecahedra, while α-cyclodextrins resulted in the original cubic crystal missing a vertex angle presenting symmetry-breaking behavior. The crystal structures of rhombic dodecahedra and angle-deficient crystals were confirmed through X-ray crystallography, and the mechanisms underlying the morphological transformation evolution were further analyzed. Our work not only provides a rare case realizing two different paths of morphological evolution in one system, but also encourages future efforts towards the evolution of artificial crystal systems in a natural way.

Metal-Organic Framework Based on Ratiometric dual-Fluorescent Sensor Using for Accurate Quantification and on-Site Visual Detection of Ascorbic Acid.

Ascorbic acid is very important to the metabolic process of the body, but excessive intake can lead to diarrhea, kidney calculi and stomach cramps. However, complicated production procedures and harsh experimental settings limit many detection methods, and a simpler and more accurate measurement method is needed. In this study, a smartphone-assisted ratiometric fluorescence sensor was developed for the portable analysis of ascorbic acid. Leveraging the catalytic properties of MIL-53(Fe) to expedite the conversion of H2O2 into hydroxyl radicals, thereby facilitating the oxidation of o-phenylenediamine and terephthalic acid bridging ligand. The sensor showcased exceptional sensitivity in detecting ascorbic acid within a linear range of 0.3-100 µM, boasting an impressive limit of detection at 0.15 µM. Furthermore, through the utilization of color extraction RGB values captured by smartphones, accurate detection of ascorbic acid was achieved with a detection limit of 0.4 µM. Real fruit samples exhibited robust spiked recovery rates ranging from 91 to 119%, accompanied by relative standard deviations ≤ 4.7%. The MIL-53(Fe) nanozyme-based smartphone-assisted ratiometric fluorescence sensor offers an ascorbic acid fluorescence detection device that is visible, accurate, sensitive, and reasonably priced.

In Situ Defect Engineering of Fe-MIL for Self-Enhanced Peroxidase-Like Activity.

Defect engineering is an effective strategy to enhance the enzyme-like activity of nanozymes. However, previous efforts have primarily focused on introducing defects via de novo synthesis and post-synthetic treatment, overlooking the dynamic evolution of defects during the catalytic process involving highly reactive oxygen species. Herein, a defect-engineered metal-organic framework (MOF) nanozyme with mixed linkers is reported. Over twofold peroxidase (POD)-like activity enhancement compared with unmodified nanozyme highlights the critical role of in situ defect formation in enhancing the catalytic performance of nanozyme. Experimental results reveal that highly active hydroxyl radical (•OH) generated in the catalytic process etches the 2,5-dihydroxyterephthalic acid ligands, contributing to electronic structure modulation of metal sites and enlarged pore sizes in the framework. The self-enhanced POD-like activity induced by in situ defect engineering promotes the generation of •OH, holding promise in colorimetric sensing for detecting dichlorvos. Utilizing smartphone photography for RGB value extraction, the resultant sensing platform achieves the detection for dichlorvos ranging from 5 to 300 ng mL-1 with a low detection limit of 2.06 ng mL-1. This pioneering work in creating in situ defects in MOFs to improve catalytic activity offers a novel perspective on traditional defect engineering.