Search

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]

During the development of Zn-air batteries, designing an affordable, efficient and stable electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) presents a great challenge. Fe2O3 exhibits ORR and OER activities, but when used as a cathode material in Zn-air batteries, its activity requires further improvement. To achieve this goal, Ni is doped into Fe2O3 hexagonal nanorods, derived from a metal-organic framework (MOF) precursor, and further modified by N-doped carbon nanotubes. In ORR, its half-wave potential achieves 0.946 and 0.716 V in alkaline and neutral electrolytes, respectively. In OER, it requires 388 mV to obtain 10 mA cm-2 in an alkaline electrolyte. As illustrated by theoretical calculation, Ni-doping raises the d-band center of Fe2O3, which enhances its adsorption towards relevant oxygen species in electrocatalysis. This improves its ORR and OER activities. Based on these merits, the Zn-air battery is assembled with an alkaline electrolyte. At 10 mA cm-2, its specific capacity and energy density reach 819.8 mA h g-1 and 960.1 W h kg-1, respectively. This battery remains stable after a long time of charge and discharge. In neutral electrolytes, its promising discharge performance is also well retained. This work develops an effective approach to improve ORR and OER activities of Fe2O3-based cathode materials in Zn-air batteries. [ABSTRACT FROM AUTHOR]

The postsynthetic metalation (PSM) of metal-organic frameworks (MOFs) with intrinsic metal binding sites is an intriguing strategy to introduce catalytic function into MOFs. The spatial distribution of the catalytic sites within the MOF crystal will affect the efficiency of the material, but the factors that govern depth distribution of the introduced metal sites are often not well understood. Herein, we employ Rutherford backscattering spectrometry (RBS) to investigate the metal distribution in a series of post-synthetically metalated mixed linker bpdc/BPY UiO-67 (UiO = Universitet i Oslo, bpdc = biphenyl-dicarboxylate, BPY = 2,2'-bipyridine-5,5'-dicarboxylate) single crystals as a function of linker ratio and metalation time. The RBS spectra reveal large differences in the depth distribution of inserted Ni2+ ions, and core/shell architectures are observed in high BPY materials at shorter incubation times. The incubation times to achieve uniform metal incorporation increases with increasing BPY ratios in the materials, suggesting that the presence of the BPY linkers slow down metal uptake. We propose a combination of ionic interactions and pore clogging, where coordinated ions reduce the available pore space for further ions to diffuse deeper into the framework as reasons for the observed trends. The observations are likely relevant for other mixed-linker MOF systems, and understanding the effect that linker ratios have on PSM and cation distribution will aid in future optimizations of catalytic MOFs. [ABSTRACT FROM AUTHOR]

Treatment of heavy metal pollution in complexed states within water bodies presents significant challenges in the current water treatment field. Adsorption as a means for the removal of heavy metals is characterized by its simplicity of operation, stable effluent, and minimal equipment requirements. Metal–organic frameworks (MOFs) as adsorbents hold significant interest for applications in water treatment. In this study, we investigated a green synthesis approach for the ball-milling pretreated synthesis of UiO-66(Zr) at room temperature, abbreviated as UiO-66(Zr)-rm. Besides having the same thermal stability and crystal structure as the product from microwave-assisted synthesis (UiO-66(Zr)-mw), the resulting UiO-66(Zr)-rm features smaller particle size and superior mesoporous structure. The adsorption efficiency and mechanism for removing EDTA-chelated copper (EDTA–CuII), a complexed heavy metal in water, were extensively analyzed. UiO-66(Zr)-rm presented a maximum adsorption capacity over EDTA–CuII of 43 mg g−1 and a much higher adsorption rate (0.16 g (mg h)−1) than UiO-66(Zr)-mw (0.06 g (mg h)−1). Hierarchically mesostructured defects allow the sorbate to have more effective diffusion in a shorter time to achieve faster adsorption kinetics. Benefiting from the mild synthesis conditions and nontoxic solvents, UiO-66(Zr) has the potential to be produced at a scaled-up level, thereby exhibiting excellent adsorption performance for the removal of complexed heavy metals in the future. [ABSTRACT FROM AUTHOR]

A novel MOF named [Zn2(L)(DMF)] was synthesized using solvothermal methods from the reaction of the new linker (4,4′,4′′-(4,4′,4′′-(benzene-1,3,5-triyltris(methylene))tris(3,5-dimethyl-1H-pyrazole-4,1-diyl))tribenzoic acid) and Zn(NO3)2·6H2O. This new MOF was characterized by means of different techniques: powder X-ray diffraction, N2 adsorption and desorption isotherms, thermogravimetric analysis, and scanning electron microscopy. Furthermore, suitable crystals were obtained, which allowed us to perform the X-Ray structure determination of this MOF. The capability of these new MOF to adsorb CO2 at different temperatures was measured and its isosteric enthalpy of adsorption was calculated. The novel MOF shows an uncommon node composed of a Zn3(–COO)6(DMF)2, and the asymmetric unit contains one crystallographically independent linker, one DMF molecule, and two Zn atoms. The [Zn2(L)(DMF)] MOF is a microporous material with high crystallinity and stability up to 250 °C. The multiple nitrogenated pyrazole linkers in its framework enhance its CO2 adsorption capabilities. This material exhibits a low CO2 isosteric enthalpy of adsorption (Hads), comparable to previously reported values for similar nitrogenated materials. All the observed CO2 adsorption capacities were further supported by DFT calculations. [ABSTRACT FROM AUTHOR]

We report on the synthesis and high ionic conductivity of a highly crystalline Mg2+-containing metal–organic framework (MOF) with Type A feature (i.e., anionic framework having Mg2+ as a counter cation). We synthesized Mg[Zr(C14H3O8)2] (SU-102-Mg) through ion exchange reaction. SU-102-Mg showed a high ionic conductivity of 3.6 × 10−5 S cm−1 (25 °C, under MeCN vapor). [ABSTRACT FROM AUTHOR]

Antibiotic resistance is a significant global concern, necessitating the development of either new antibiotics or advanced delivery methods. With this in mind, we report on the synthesis and characterisation of a new family of Metal–Organic Frameworks (MOFs), OnG6 MOFs, designed to act as multi-drug carriers for bacterial infection treatment. OnG6 is based on the pro-drug 4,4′-azodisalicylic acid (AZDH4), which in vivo produces two equivalents of para-aminosalicylic acid (ASA), a crucial drug for M. tuberculosis treatment. X-ray and computational studies revealed that OnG6 MOFs are mesoporous MOFs with etb topology and an [M2(AZD)] formula (M = Zn, OnG6-Zn; Mg, OnG6-Mg; Cu, OnG6-Cu; and Co, OnG6-Co), featuring 1-dimensional channel type pores of 25 Å diameter. OnG6 MOFs are the first reported MOFs bearing the ligand AZDH4, joining the family of mesoporous MOFs arranged in a honeycomb pattern. They absorb isoniazid (INH) and ciprofloxacin (CIPRO) with the former being a specific antibiotic for M. tuberculosis, and the latter being a broader-spectrum antibiotic. The stability of the MOFs and their capacity for antibiotic uptake depend on the nature of the metal ion, with OnG6-Mg demonstrating the highest drug absorption. The antimicrobial activity of these species was assessed against S. aureus and E. coli, revealing that the carriers containing CIPRO displayed optimal efficacy. [ABSTRACT FROM AUTHOR]

Two novel Ce(III) metal organic frameworks (MOFs) with formulas [Ce(5Meip)(H-5Meip)]nGR-MOF-17 and [CeCl(5Meip)(DMF)]nGR-MOF-18 (5Meip = 5-methylisophthalate, DMF = N,N-dimethylformamide) have been synthesized, forming 3-dimensional frameworks. Magnetic measurements show that both compounds present field-induced slow magnetic relaxation under a small applied dc field. For GR-MOF-17, the temperature dependence of relaxation times is best described by a Raman mechanism, whereas for GR-MOF-18, relaxation occurs through a combination of Raman and local-mode pathways. Moreover, when avoiding short Ce⋯Ce interactions by magnetic dilution in GR-MOF-17@La and GR-MOF-18@La, only the local-mode mechanism is responsible for magnetic relaxation. Photophysical studies show the occurrence of ligand-centred luminescence in both compounds and phosphorescence emission at low temperature for GR-MOF-17. [ABSTRACT FROM AUTHOR]

A novel sheet-like tin-based metal–organic framework exhibited a specific capacity for lithium storage as high as 1033.3 mAh g−1 at 200 mA g−1 with excellent cycling stability. This framework, due to its unique porous structure and multiple lithium storage sites, could better cope with challenges occurring during lithium insertion/extraction than could traditional tin materials. [ABSTRACT FROM AUTHOR]

Built from L -histidine amino acid ligand and cadmium ions, two new 3D chiral metal–organic frameworks, [α-Cd(HIS)] (1) and [β-Cd(HIS)] (2), which contain metal-histidine bonds mimicking the structure features of carbonic anhydrase, demonstrate interesting properties of catalyzing the hydrolysis of p-nitrophenylacetate (p-NPA) to para-nitrophenol (p-NP). [ABSTRACT FROM AUTHOR]

A two-dimensional zirconium-based metal–organic framework (2D Zr-MOF), ZrBTB (BTB = 1,3,5-tri(4-carboxyphenyl)benzene), is used as a platform to simultaneously immobilize terbium ions and europium ions with tunable ratios on its hexa-zirconium nodes by a post-synthetic modification. The crystallinity, morphology, porosity and photoluminescence (PL) properties of the obtained 2D Zr-MOFs with various europium-to-terbium ratios are investigated. With the energy transfer from the excited BTB linker to the installed terbium ions and the energy transfer from terbium ions to europium ions, a low loading of immobilized europium ions and a high loading of surrounding terbium ions in the 2D Zr-MOF result in the optimal PL emission intensities of europium; this phenomenon is not observable for the physical mixture of both terbium-installed ZrBTB and europium-installed ZrBTB. The role of installed terbium ions as efficient mediators for the energy transfer from the excited BTB linker to the installed europium ion is confirmed by quantifying PL quantum yields. As a demonstration, these materials with modulable PL characteristics are applied for the ratiometric detection of D2O in water, with the use of the stable emission from the BTB linker as the reference. With the strong emission of immobilized europium ions and the good dispersity in aqueous solutions, the optimal bimetal-installed ZrBTB, Eu-Tb-ZrBTB(1 : 10), can achieve the sensing performance outperforming those of the terbium-installed ZrBTB, europium-installed ZrBTB and the physical mixture of both. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have emerged as promising electrode materials for supercapacitors (SCs) due to their highly porous structures, tunable chemical compositions, and diverse morphologies. However, their applications are hindered by low conductivity and poor cycling performance. A novel approach for resolving this issue involves the growth of layered double hydroxides (LDHs) using MOFs as efficient templates or precursors for electrode material preparation. This method effectively enhances the stability, electrical conductivity, and mass transport ability of MOFs. The MOF-derived LDH exhibits a well-defined porous micro-/nano-structure, facilitating the dispersion of active sites and preventing the aggregation of LDHs. Firstly, this paper introduces synthesis strategies for converting MOFs into LDHs. Subsequently, recent research progress in MOF-derived LDHs encompassing pristine LDH powders, LDH composites, and LDH-based arrays, along with their applications in SCs, is overviewed. Finally, the challenges associated with MOF-derived LDH electrode materials and potential solutions are discussed. [ABSTRACT FROM AUTHOR]

Here we describe the synthesis of a compositional series of metal–organic framework crystalline-inorganic glass composites (MOF-CIGCs) containing ZIF-8 and an inorganic phosphate glass, 20Na2O–10NaCl–70P2O5, to expand the library of host matrices for metal–organic frameworks. By careful selection of the inorganic glass component, a relatively high loading of ZIF-8 (70 wt%) was achieved, which is the active component of the composite. A Zn⋯O–P interfacial bond, previously identified in similar composites/hybrid blends, was suggested by analysis of the total scattering pair distribution function data. Additionally, CO2 and N2 sorption and variable-temperature PXRD experiments were performed to assess the composites' properties. [ABSTRACT FROM AUTHOR]

A hydrogen-bonded three-dimensional porous metal–organic framework [Mg(H2PCD)2(H2O)2]·2H2O (denoted as Mg-MOF·2H2O; H3PCD = 9-(2-(ethoxy(hydroxy)phosphonyl)ethyl)-9H-carbazole-3,6-dicarboxylic acid) was synthesized by the reactions of H3PCD and Mg(II) under solvothermal conditions. The free carboxylate group was maintained in the pore surface by adjusting the acidic reaction conditions. The highly stable Mg-MOF exhibits excellent performance for lead(II) sensing and removal from aqueous solutions. [ABSTRACT FROM AUTHOR]

The increasing CO2 emissions and their direct impact on climate change due to the greenhouse effect are environmental issues that must be solved as soon as possible. Metal–organic frameworks (MOFs) are one class of crystalline adsorbent materials that are thought to have enormous potential in CO2 capture applications. In this research, the effect of changing the metal center between Zr(IV), Ce(IV), and Hf(IV), and the linker between BDC and PDC has been fully studied. Thus, the six UiO-66 isoreticular derivatives have been synthesized and characterized by FTIR, PXRD, TGA, and N2 adsorption. We also report the BET surface area, CO2 adsorption capacities, kinetics, and the adsorption isosteric heat (Qst) of the UiO-66 derivatives mentioned family. The CO2 adsorption kinetics were evaluated using pseudo-first order, pseudo-second order, Avrami's kinetic models, and the rate-limiting step with Boyd's film diffusion, interparticle diffusion, and intraparticle diffusion models. The isosteric heats of CO2 adsorption using various MOFs are in the range 20–65 kJ mol−1 observing differences in adsorption capacities between 1.15 and 4.72 mmol g−1 at different temperatures due to the electrostatic interactions between CO2 and extra-framework metal ions. The isosteric heat of adsorption calculation in this report, which accounts for the unexpectedly high heat released from Zr-UiO-66-PDC, is finally represented as an increase in the interaction of CO2 with the PDC linker and an increase in Qst with defects. [ABSTRACT FROM AUTHOR]

The capture and conversion of carbon dioxide (CO2) into valuable chemical products under mild conditions is an important and challenging approach for contemporary industry. Carboxylic acid ligands are widely used in the development of functionalized metal organic framework materials due to their excellent stability. Herein, a novel mixed-metal organic framework Cu-TCPP(Fe) was assembled from iron-(Fe)-porphyrin ligands, which can efficiently catalyze the reaction of propargylic amines and CO2 to synthesize 2-oxazolidinones. [ABSTRACT FROM AUTHOR]

We present the synthesis and magneto-thermal properties of carborane-based lanthanide metal-organic frameworks (MOFs) with the formula {[(Ln)3(mCB-L)4(NO3)(DMF)n]·Solv}, where Ln = Dy or Tb, characterized by dc and ac susceptibility, X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and heat capacity measurements. The MOF structure is formed by polymeric 1D chains of Ln ions with three different coordination environments (Ln1, Ln2, Ln3) running along the b-axis, linked by carborane-based linkers thus to provide a 3D structure. Static magnetic measurements reveal that these MOFs behave at low temperature as a system of S* = 1/2 Ising spins, weakly interacting ferromagnetically along the 1D polymeric chain (J*/kB = +0.45 K (+0.5 K) interaction constant estimated for Dy-MOF (Tb-MOF)) and coupled to Ln ions in adjacent chains through dipolar antiferromagnetic interactions. The Dy MOF exhibits slow relaxation of magnetization through a thermally activated process, transitioning to quantum tunneling of the magnetization at low temperatures, while both compounds exhibit field-induced relaxation through a very slow, direct process. The maximum magnetic entropy changes (-ΔSmaxm) for an applied magnetic field change of 2-0 T are 5.71 J kg-1 K-1 and 4.78 J kg-1 K-1, for Dy and Tb MOFs, respectively, while the magnetocaloric effect (MCE) peak for both occurs at T ~ 1.6 K, approximately double that for the Gd counterpart. [ABSTRACT FROM AUTHOR]

Interfacial engineering emerges as a potent strategy for regulating the catalytic reactivity of metal phosphides. Developing a facile and cost-effective method to construct bifunctional metal phosphides for highly efficient electrochemical overall water splitting remains an essential and challenging issue. Here, a multiphase transition metal phosphide is constructed through the direct phosphorization of a Ni–Co metal–organic framework grown on nickel foam (Ni–Co-MOF/NF), which is prepared by utilizing nickel foam as conductive substrate and nickel source. The resulting transition metal phosphide manifests a pillar-layered morphology, wherein CoP, Ni2P, and Ni5P4 nanoparticles are embedded within each carbon sheet and these carbon sheets assemble into a pillar-shaped structure on the nickel foam (Ni2P–Ni5P4–CoP–C/NF). The heterogeneous Ni2P-Ni5P4–CoP–C/NF with multiple interfaces serves as a highly efficient bifunctional electrocatalyst with overpotentials of −100 mV and 293 mV in the hydrogen evolution reaction and oxygen evolution reaction, respectively, at 50 mA cm−2 in alkaline media. This superior catalytic performance should mainly be ascribed to its enriched active centers and multiphase synergy. When directly applied for alkaline overall water splitting, the Ni2P–Ni5P4–CoP–C/NF couple demonstrates satisfactory activity (1.55 V @10 mA cm−2) along with sustained durability over 18 hours. This method brings fresh enlightenment to the economical and controllable preparation of multi-metal phosphides for energy conversion. [ABSTRACT FROM AUTHOR]

The increasing utilization of hydrazine and its derivatives across diverse sectors highlights the pressing need for efficient detection methods to safeguard human health and the environment. Likewise, nicardipine, a widely used medication for heart diseases, necessitates accurate sensing techniques for clinical research and therapeutic monitoring. Here, we propose a novel approach using a naphthalimide-functionalized Zr-MOF as a fluorometric probe capable of detecting both hydrazine and nicardipine in aqueous medium. Our designed probe exhibited a significant 31-fold increase in fluorescence intensity upon interaction with hydrazine. At the same time, nicardipine induced 86% fluorescence quenching with an exceptionally rapid response time (100 s for hydrazine and 5 s for nicardipine). The designed probe has the ability to detect both analytes at nanomolar concentrations (LOD for hydrazine is 1.11 nM while that for nicardipine is 9.6 nM). Investigation across various wastewater samples and pH conditions further validated its practical utility. The mechanism behind fluorometric sensing of nicardipine was thoroughly investigated using modern instrumentation. Our study presents a versatile and effective approach for detecting hydrazine and nicardipine, addressing crucial needs in both industrial and biomedical contexts. [ABSTRACT FROM AUTHOR]

This study explores the utilization of metal–organic frameworks (MOFs), particularly those incorporating lanthanide-based elements for their fluorescence capabilities, to create an advanced barcode system. By exploiting the modular nature of MOFs, we have developed a material capable of dynamic information encoding and robust against counterfeiting efforts. We introduce a novel barcode prototype that exhibits visible color shifts and fluorescence modulation when exposed to a specific sequence of chemical and thermal stimuli. The barcode is composed of MOF-808, which is modified with transition metals like iron or cobalt, and europium cations. These components are embedded within polyvinylidene fluoride (PVDF) to form a composite. This embedding process ensures that the MOF particles remain reactive to specific trigger molecules, enabling a distinct read-out sequence. The decoding process, involving exposure to ammonia, heating at 120 °C, and treatment with HCl, triggers observable changes in fluorescence and color, depending on the transition metal used. Our investigations with Eu,Co-MOF-808, and Eu,Fe-MOF-808 composites have resulted in the creation of a barcode prototype that demonstrates the feasibility of using europium-modified and unmodified transition metal modified MOF-808@PVDF composites for enhanced security applications. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) featuring zirconium-based clusters are widely used for the development of functionalized materials due to their exceptional stability. In this study, we report the synthesis of a novel N,N,N-ligand compatible with a biphenyl dicarboxylic acid-based MOF. However, the resulting copper(I) complex exhibited unexpected coordination behaviour, lacking the intended trifold coordination motif. Herein, we demonstrate the successful immobilization of a bioinspired ligand within the MOF, which preserved its crystalline and porous nature while generating a well-defined copper site. Comprehensive spectroscopic analyses, including X-ray absorption, UV/Vis, and infrared spectroscopy, were conducted to investigate the copper site and its thermal behaviour. The immobilized ligand exhibited the desired tridentate coordination to copper, providing access to a coordination motif otherwise unattainable. Notably, water molecules were also found to coordinate to copper. Upon heating, the copper centre within the MOF exhibited reversible dehydration, suggesting facile creation of open coordination sites. Furthermore, the copper site displayed reduction at elevated temperatures and subsequent susceptibility to oxidation by molecular oxygen. Lastly, both the molecular complexes and the MOF were evaluated as catalysts for the oxidation of cyclohexane using hydrogen peroxide. This work highlights the successful immobilization of a bioinspired ligand in a zirconium-based MOF, shedding light on the structural features, thermal behaviour, and catalytic potential of the resulting copper sites. [ABSTRACT FROM AUTHOR]

Highly connected molecular building blocks (MBBs) have been demonstrated to play a crucial role in reticular chemistry, particularly in predicting the topologies of metal–organic frameworks. Metal phosphonate clusters exhibit considerable advantages in constructing high-connectivity MBBs, owing to the multiple coordination modes offered by phosphonic ligands. Herein, four metal (M = CoII, MnII) phosphonocarboxylate frameworks (CoPCF-1,2 and MnPCF-1,2) were successfully prepared under solvothermal conditions by utilizing the phosphonocarboxylic ligand, 4′-phosphonobiphenyl-3,5-dicarboxylic acid (H4pbpdc), and their structural characterization was performed using single-crystal X-ray diffraction (SCXRD). The structures feature a duodenary nuclear M12(µ3-OH)2(CO2)12(PO3)6(DMF)6/(CH3COO)4.5 cluster, bearing resemblance to the well-known Wells–Dawson ion from polyoxometallate chemistry. It is the first time a Wells–Dawson type cage has served as an 18-connected molecular building block, forming two kinds of porous metal phosphonocarboxylate frameworks with novel (3,18)-connected gez and gea topologies. Their permanent porosities were confirmed through N2 adsorption studies. Notably, the MBB Co12 cluster-based CoPCF-1 shows a loss and recovery process of µ3-OH through single-crystal-to-single-crystal (SCSC) transformation. The magnetic properties of the four compounds exhibit antiferromagnetic behavior. [ABSTRACT FROM AUTHOR]

While there are myriad ways to construct metal–organic framework (MOF) based catalysts, the introduction of catalytic functionality via covalent post-synthesis functionalization (PSM) offers multiple advantages: (i) a wide range of different catalyst types are generated from a handful of well-known parent MOFs, (ii) MOF catalyst properties can be systematically tuned while changing few variables, and (iii) catalytically active functional groups that would otherwise interfere with MOF assembly can be introduced facilely. This last advantage is particularly crucial for our quest to generate MOF active sites that are decorated with multiple functional groups capable of cooperative activity, analogous to enzyme active sites. [ABSTRACT FROM AUTHOR]

While metal–organic framework (MOF) photocatalysts have demonstrated a unique Cr(VI) photoreduction capability in recent decades, their performance is still insufficient for practical applications because of their low Cr(VI) uptake and poor visible light response. To cope with these drawbacks, a new OH-modified Zr-based MOF, termed HCMUE-1, was successfully prepared via a solvothermal method in this work. The complete characterization of HCMUE-1 was performed through various techniques, including powder X-ray diffraction (PXRD), Raman spectroscopy, Fourier transform infrared (FT-IR), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), scanning electron microscopy combined with energy-dispersive X-ray (SEM-EDX), and X-ray photoelectron spectroscopy (XPS). The obtained data exhibited the excellent Cr(VI) photoreduction efficiency of HCMUE-1, reaching up to 98% after 90 min and almost 100% after 120 min under visible light illumination in a low acidic medium. Noteworthily, HCMUE-1 retained the same Cr(VI) removal rate for at least seven cycles without considerable loss. Further experimental investigations demonstrated that the structural stability and surface morphology of HCMUE-1 were retained after photoreduction. Moreover, the photocatalytic reduction mechanism of Cr(VI) to Cr(III) was interpreted through a series of systematic experimental measurements. These results indicate that HCMUE-1 possesses potential as an efficient photocatalyst for reducing toxic Cr(VI) species from wastewater in real-life conditions. [ABSTRACT FROM AUTHOR]

The electrochemical reduction of CO2 to CO is a powerful approach to achieving carbon neutrality. Herein, we report a five-nuclear copper cluster-based metal–azolate framework CuTz-1 as an electrocatalyst for the electrochemical CO2 reduction reaction. It achieved a faradaic efficiency (FE) of 62.7% for yielding CO with a partial current density of −35.1 mA cm−2 in flow cell device, which can be preserved for more than ten hours with negligible changes of the current density and FE(CO). Studies of electrocatalytic mechanism studies revealed that the distance of Cu–N was increased, and the coordination number of the Cu ion was reduced, while the oxidation state of Cu was decreased after the electrocatalysis. These findings offer valuable insights into structural changes that influence the performance of the catalyst during the process of the electrochemical reduction of CO2 process. [ABSTRACT FROM AUTHOR]

Three new isostructural MOFs (ZnTIA, CoTIA and CdTIA) were synthesized by the solvothermal synthesis of the organic linker 5-triazole isophthalic acid (5-TIA) with the transition metals Zn(II), Co(II) and Cd(II) in the presence of the structure directing agent tetramethyl ammonium chloride (TMA). These three MOFs were characterized thoroughly by ScXRD, PXRD, FT-IR, TGA, BET and SEM. They have excellent thermal and water stabilities. Among all these MOFs mentioned, pristine CoTIA exhibited excellent electrocatalytic activity toward the oxygen evolution reaction (OER). It exhibits a Tafel slope of 68.9 mV dec−1 with an overpotential of 337 mV at 10 mA cm−2 current density. The OER activity of the CoTIA MOF is relatively equivalent to that of the state-of-the-art catalyst (RuO2). Furthermore, the mechanical stability of crystalline ZnTIA, CoTIA and CdTIA MOFs was tested under ball mill pressure. The result showed that all the MOFs exhibit low tolerance to mechanical force because their structure was highly distorted or collapsed under such pressure, which is reflected by their poor electrocatalytic OER activity. [ABSTRACT FROM AUTHOR]

Since exhaled ammonia (NH3) is one of the metabolic markers of liver and kidney diseases, ammonia visual sensing materials in humid environments have received extensive attention and investigation. Herein, through a tailor-made pore environment provided by metal–organic framework (MOF) materials (CH3-Cu(BDC)), we achieved NH3 anti-interference sensing with apparent color changing under humid conditions. With methyl (CH3–) functionalization, CH3-Cu(BDC) demonstrated a strong response for trace ammonia and showed high selectivity under a humid environment. Grand canonical Monte Carlo (GCMC) simulations indicated that CH3-Cu(BDC) showed stronger attraction towards NH3 molecules than H2O. Benefiting from the target changing coordination environment, CH3-Cu(BDC) showed a rapid response and simple analysis properties for patients' exhaled air. The strategy used in this study not only provides a demonstration case for NH3 colorimetric sensing with high humidity and anti-interference but also introduces a new method for painless and quick exhaled breath analysis for diagnosis of patients with kidney and liver diseases. [ABSTRACT FROM AUTHOR]

The synthesis of cyclic carbonates through cycloaddition reactions between epoxides and carbon dioxide (CO2) is an important industrial process. Metal-Organic Frameworks (MOFs) have functional and ordered pore structures, making them attractive catalysts for converting gas molecules into valuable products. One approach to enhance the catalytic activity of MOFs in CO2 cycloaddition reactions is to create open metal sites within MOFs. In this study, the amino-functionalized rare earth Gd-MOF (Gd-TPTC-NH2) and its ionic liquid composite catalysts (Gd-TPTC-NH-[BMIM]Br) were synthesized using 2'-amino-[1,1':4',1"-terphenyl]-3,3",5,5"-tetracarboxylic acid (H4TPTC-NH2) as the ligand. The catalytic performance of these two catalysts was observed in the cycloaddition reaction of CO2 and epoxides. Under the optimized reaction conditions, Gd-TPTC-NH-[BMIM]Br can effectively catalyze the cycloaddition reaction of a variety of epoxide substrates with good to excellent yields of cyclic carbonate products. Comparatively, epichlorohydrin and epibromohydrin, which possess halogen substituents, promote higher yields of cyclic carbonates due to the electron-withdrawing nature of Cl and Br substituents. Additionally, the Gd-TPTC-NH- [BMIM]Br catalyst demonstrated good recyclability and reproducibility, maintaining its catalytic activity without any changes in its structure or properties after five reuse cycles. [ABSTRACT FROM AUTHOR]

The effective integration of nanomaterials with underlying current collectors is a key factor affecting the performance of nonenzymatic glucose sensors, where an inappropriate integration structure often leads to poor electron transport and instability. In this work, a seamless integrated electrode was constructed by the in situ immobilizing of a nickel-based metal-organic framework (Ni-MOF) on a three-dimensional (3D) conductive nickel foam (NF) for highly sensitive and durable glucose sensing. Facilitated by a rapid microwave-assisted reaction, a robust interfacial interaction between the Ni-MOF and the substrate was established through in situ conversion from nickel oxide (NiO). The fabricated Ni-MOF/NF electrode exhibits an excellent limit of detection (LOD) of 2.65 μM and an impressive sensitivity (14.31 mA cm-2 mM-1) within the linear range (4-576 μM), which is significantly boosted compared with that of an electrode prepared by a typical drop-casting method (3.56 mA cm-2 mM-1 in 4-1836 μM). Characterization and electrochemical tests reveal that this integrated structure on the one hand contributes to fast electron transport and thus has enhanced sensitivity and on the other hand leads to exceptional durability with its structural integrity maintained under bending, shaking, and ultrasonication. Moreover, this seamless integration method was also employed to immobilize the Ni-MOF converted from the pre-chemically deposited NiO layer on another type of substrate, 3D carbon paper (CP), demonstrating the versatility of this facile strategy in creating diverse electrochemical electrodes for applications beyond glucose sensing. [ABSTRACT FROM AUTHOR]

In order to improve the oxidative desulfurization (ODS) performance of MOF materials, an effective way is to convert a microporous MOF into a hierarchical porous MOF (HP-MOF) by utilizing the linker selective retention strategy. Herein, UiO-66 with the introduction of an unstable linker ligand (dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate, dhtz) can selectively remove dhtz ligands to form HP-MOF (HP-UiO-66-dhtz) through heat treatment at high temperature. While maintaining the original structure of UiO-66, HP-UiO-66-dhtz features mesopores and abundant Lewis acid sites, showing excellent ODS performance for diphenylthiophene (DBT). [ABSTRACT FROM AUTHOR]

A new magnesium-based metal–organic framework with unprecedented short-chain secondary building units and ultra-micropore channels approaching the kinetic diameters of Xe is fabricated by decorating methyl groups on ligands. Due to the contracted pores, this MOF exhibits very high selectivity values for Xe/Kr, which ranks it among the top porous absorbents. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have emerged as a promising class of materials for solar-driven hydrogen peroxide (H2O2) generation due to their porosity, large surface area and designable molecular building blocks; however, producing H2O2 from oxygen and water without sacrificial agents remains a major challenge. Herein, we have constructed two UiO-67-type MOFs, UiO-67-NH2 and UiO-67-(NH2)2, by a solvothermal method using 2-amino-4,4′-biphenyldicarboxylic acid and 2,2′-diamino-4,4′-biphenyldicarboxylic acid as ligands, respectively. A variety of photochemical measurements have shown that the introduction of diamino groups into UiO-67-(NH2)2 not only enhances its absorption ability for visible light, but also facilitates the separation of photogenerated electron/hole pairs. Consequently, compared to monoamino-functionalized UiO-67-NH2, UiO-67-(NH2)2 exhibits a 5.5 times higher H2O2 production rate in pure water for 1 h. A two-step one-electron oxygen reduction reaction pathway for photocatalytic H2O2 production was suggested based on a series of control experiments and active species trapping tests by electron paramagnetic resonance spectra. This work provides new insights into the regulation of functionalized MOF ligands at the molecular level and a catalytic mechanism towards MOF-based photocatalysts for H2O2 production with high activity. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOF) are a subclass of porous framework materials that have been used for a wide variety of applications in sensing, catalysis, and remediation. Among these myriad applications is their remarkable ability to capture substances in a variety of environments ranging from benign to extreme. Among the most common and problematic substances found throughout the world's oceans and water supplies is [UO2]2+, a common mobile ion of uranium, which is found both naturally and as a result of anthropogenic activities, leading to problematic environmental contamination. While some MOFs possess high capability for the uptake of [UO2]2+, many more of the thousands of MOFs and their modifications that have been produced over the years have yet to be studied for their ability to uptake [UO2]2+. However, studying the thousands of MOFs and their modifications presents an incredibly difficult task. As such, a way to narrow down the numbers seems imperative. Herein, we evaluate the binding behaviors as well as identify the specific binding sites of [UO2]2+ incorporated into six different Zr MOFs to elucidate specific features that improve [UO2]2+ uptake. In doing so, we also present a method for the determination and verification of these binding sites by Anomalous wide-angle X-ray scattering, X-ray fluorescence, and X-ray absorption spectroscopy. This research not only presents a way for future research into the uptake of [UO2]2+ into MOFs to be conducted but also a means to evaluate MOFs more generally for the uptake of other compounds to be applied for environmental remediation and improvement of ecosystems globally. [ABSTRACT FROM AUTHOR]

The design and synthesis of a Gd(III) metal–organic framework with the formula [Gd4(BTDI)3(DMF)4]n (JXUST-40, H4BTDI = 5,5′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalic acid) are reported hererin. Interestingly, a reversible single-crystal-to-single-crystal transition between JXUST-40 and {[Gd4(BTDI)3(H2O)4]·6H2O}n (JXUST-40a) was achieved under the stimulation of heat and solvents. Both JXUST-40 and JXUST-40a exhibited good stability when soaked in common solvents and aqueous solutions with pH values of 1–12. Magnetic studies showed that JXUST-40a has a larger magnetocaloric effect with –ΔS maxm = 26.65 J kg−1 K−1 at 2 K and 7 T than JXUST-40 due to its larger magnetic density. Structural analyses indicated that the coordinated solvent molecules play a crucial role in the coordination environment around the Gd(III) ions and the change in the framework, ultimately leading to the changes in the pore size and magnetism between JXUST-40 and JXUST-40a. In addition, both isomorphic [Dy4(BTDI)3(DMF)4]n (JXUST-41) and {[Dy4(BTDI)3(H2O)4]·6H2O}n (JXUST-41a) displayed slow magnetic relaxation behaviour. [ABSTRACT FROM AUTHOR]

Noble metal-based catalysts such as RuO2 and IrO2 are widely used in the catalysis of the OER. However, because of their high price and poor stability, it is urgent to develop transition metal-based electrocatalysts with low precious metal doping as an alternative. Layered double hydroxides (LDHs) grown on 3D metal–organic frameworks (MOFs) are ideal for doping precious metals owing to abundant defects at the heterointerface, large surface area, and intrinsic oxygen evolution activity. In this study, a novel FeNi LDH/MOF heterostructure was prepared via a two-step solvothermal method using Fe-soc-MOFs as the substrate. Subsequently, Ru was introduced through a hydrothermal process. The as-synthesized Ru@FeNi LDH/MOF has an overpotential of only 242 mV at a current density of 10 mA cm−2 and can be used in continuous electrolysis for 48 h. Its unique nanocubic core–shell structure and flower-like LDHs on its surface provide a large number of active sites, which become the key to ensuring high activity and stability. With the doping of Ru, the electronic structure was adjusted and electron transfer was accelerated, further improving electrochemical activity. This study provides a new idea for developing transition metal-based catalysts with low noble metal loading. [ABSTRACT FROM AUTHOR]

In this work, a three-dimensional bimetallic metal–organic framework (BMOF), BUC-101 (Co/Mn-H6chhc, H6chhc = cis-1,2,3,4,5,6-cyclohexane-hexacarboxylic acid, BUC = Beijing University of Civil Engineering and Architecture) was synthesized by a one-pot solvothermal method and characterized in detail by single crystal X-ray diffraction (SCXRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) element mapping analysis. BUC-101 showed excellent catalytic peroxymonosulfate (PMS) activation performance to degrade rhodamine B (RhB) without energy input. In addition, BUC-101 can maintain good stability and recyclability during the PMS activation processes, in which 99.9% RhB degradation efficiencies could be accomplished in 5 operational runs. The possible PMS activation and RhB degradation mechanisms of the BUC-101/PMS system were proposed and affirmed. [ABSTRACT FROM AUTHOR]

A newly synthesized series of bimetallic CPM-37(Ni,Fe) metal–organic frameworks with different iron content (Ni/Fe ≈ 2, 1, 0.5, named CPM-37(Ni2Fe), CPM-37(NiFe) and CPM-37(NiFe2)) demonstrated high N2-based specific SBET surface areas of 2039, 1955, and 2378 m2 g−1 for CPM-37(Ni2Fe), CPM-37(NiFe), and CPM-37(NiFe2), having much higher values compared to the monometallic CPM-37(Ni) and CPM-37(Fe) with 87 and 368 m2 g−1 only. It is rationalized that the mixed-metal nature of the materials increases the structural robustness due to the better charge balance at the coordination bonded cluster, which opens interesting application-oriented possibilities for mixed-metal CPM-37 and other less-stable MOFs. In this work, the CPM-37-derived α,β-Ni(OH)2, γ-NiO(OH), and, plausibly, γ-FeO(OH) phases obtained via decomposition in the alkaline medium demonstrated a potent electrocatalytic activity in the oxygen evolution reaction (OER). The ratio Ni : Fe ≈ 2 from CPM-37(Ni2Fe) showed the best OER activity with a small overpotential of 290 mV at 50 mA cm−2, low Tafel slope of 39 mV dec−1, and more stable OER performance compared to RuO2 after 20 h chronopotentiometry at 50 mA cm−2. [ABSTRACT FROM AUTHOR]

Due to their hazard to biological systems, it is urgent to develop materials that can rapidly and sensitively detect the concentration of H2PO4− and OCN− ions. In this work, a new CdII-based luminescent metal–organic framework with the formula [Cd(BTDB)(2,6-BBIP)]n (JXUST-47, H2BTDB = (benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid, 2,6-BBIP = 2,6-bis(benzimidazol-1-yl)pyridine) and sql topology was successfully synthesized using a mixed-ligand strategy. JXUST-47 shows good chemical and thermal stability. It also exhibits weak quenching and fluorescence blue shift for H2PO4− and red shift for OCN−, with the detection limits of 0.106 and 0.128 mM, respectively. In addition, considering the demand for H2PO4− and OCN− ion detection, by combining this with the functions of a smartphone, the chroma of photographs have been used to realize the consecutive visual detection of the concentration of these ions. [ABSTRACT FROM AUTHOR]

Oxygen evolution reaction (OER) electrocatalysts are frequently made from noble metal-based oxides like ruthenium/iridium oxides. However, because of their scarcity and high price, researchers are now focusing on creating innovative OER catalysts based on affordable transition metals that have improved electrical conductivity and accessibility to active sites. Metal–organic frameworks (MOFs), a unique class of inorganic materials with excellent physical and chemical properties, have witnessed significant progress in promising green energy systems. In this work, a novel mixed-ligand metal–organic framework [Co(μ-1κN,2κN′-BDP)(μ3-1κoo′,2κo′′2κo′′′-BTC)]n·nH2O (BDP = boron-dipyrromethene or BODIPY; BTC = benzene tricarboxylate) denoted as CoBDPMOF has been synthesized, and its composites with different carbon materials have been designed. Compared to the pristine MOF, the composites showed enhanced electrocatalytic activity toward the oxygen evolution reaction (OER) in alkaline media. In addition, the CoBDPMOF with activated carbon showed the highest OER performance with a low Tafel slope (82 mV dec−1) and the highest j600 (59.8 mA cm−2), outperforming noble metal IrO2, the OER benchmark electrocatalyst. This study presents new insights into the design and application of CoBDPMOF-based materials for energy conversion and suggests promising avenues for further research and development in electrocatalysis. [ABSTRACT FROM AUTHOR]

Due to their hazard to biological systems, it is urgent to develop materials that can rapidly and sensitively detect the concentration of H2PO4− and OCN− ions. In this work, a new CdII-based luminescent metal–organic framework with the formula [Cd(BTDB)(2,6-BBIP)]n (JXUST-47, H2BTDB = (benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid, 2,6-BBIP = 2,6-bis(benzimidazol-1-yl)pyridine) and sql topology was successfully synthesized using a mixed-ligand strategy. JXUST-47 shows good chemical and thermal stability. It also exhibits weak quenching and fluorescence blue shift for H2PO4− and red shift for OCN−, with the detection limits of 0.106 and 0.128 mM, respectively. In addition, considering the demand for H2PO4− and OCN− ion detection, by combining this with the functions of a smartphone, the chroma of photographs have been used to realize the consecutive visual detection of the concentration of these ions. [ABSTRACT FROM AUTHOR]

MIL-53 represents one of the most notable metal–organic frameworks given its unique structural flexibility and remarkable thermal stability. In this study, a shaker-type ball milling method has been developed into a facile and generalizable synthetic strategy to access a family of MIL-53 type materials under ambient conditions. During the explorations of [M(OH)(fumarate)] (M = Al, Ga, and In), we report a positive correlation between the metal–ligand (M–L) bond reversibility and the size of resultant crystallites under the mechanochemical process. The more kinetically labile the M–L bond is, the larger the afforded crystallite size is. [ABSTRACT FROM AUTHOR]

In this work, nickel-catecholate (Ni-CAT) nanorods were in situ compounded on graphene oxide (GO) to form a composite Ni-CAT@GO (NCG) with a special "blanket-shape" structure, which was used as an electrode material for supercapacitors. The morphology of Ni-CATs in situ grown on GO was modulated by introducing various contents of GO. With increasing GO, the length of nanorods of Ni-CATs is obviously shortened, and the charge transfer resistance of NCG is significantly reduced as the GO content is relatively low while it increases with further addition of GO, because excessive GO in NCG results in smaller crystal sizes accompanied by smaller stacking pores. Both the over-long Ni-CAT nanorods and the smaller stacking pores can restrict the accessible surface areas for the electrolyte. Optimal nanorod sizes are crucial to achieve good electrochemical performance for electrode materials. Galvanostatic charge–discharge analysis of NCG electrodes shows that their capacity initially increases and then decreases with the addition of more and more GO, and Ni-CAT@GO-0.5 (NCG0.5) with minimal charge transfer resistance exhibits the best electrochemical performance. The results demonstrate that the NCG0.5 electrode with optimal morphology possesses an excellent capacitance of 563.8 F g−1 at 0.5 A g−1 and a good rate performance of 61.9% at 10 A g−1, indicating that Ni-CAT@GO is a new type of promising electrode material for supercapacitors based on conductive metal–organic frameworks. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have found wide applications in the field of supercapacitors due to their highly controllable porous structure, big specific surface area, and abundant chemical functional groups. MOF-on-MOF hybrids not only enhance the composition of MOFs (such as ligands and/or metal centers) but also provide greater structural diversity. By utilizing MOFs as precursors for preparing sulfides, the unique characteristics and inherent structure of MOFs are preserved but their conductivity and capacitance are enhanced. This study successfully synthesized hollow-structured Ni3S4@Co3S4 derived from an Ni-MOF@ZIF-67 hybrid structure, where the Ni-MOF serves as the core and ZIF-67 as the satellite. The Ni3S4@Co3S4 electrode demonstrated a specific capacity as high as 747.3 C g−1 at 1 A g−1, and it could still maintain 77% of its initial capacity at 10 A g−1. Furthermore, the assembled Ni3S4@Co3S4//AC hybrid supercapacitor (HSC) device achieved a maximum energy density of 30.8 W h kg−1 when the power density was 750 W kg−1. The device exhibited remarkable cycling durability, retaining 85.4% of its initial capacitance after 5000 cycles. Therefore, the derived functional materials based on MOF-on-MOF provide a more scalable and promising approach for the preparation of efficient electrode materials. [ABSTRACT FROM AUTHOR]

The pyrolysis of metal–organic frameworks (MOFs) has emerged as a promising route to synthesize carbon/metal oxide-based materials with diverse phase compositions, morphologies, sizes and surface areas. In this paper, 1,3,5-benzoic acid (BTC) and 2,4,6-tri(4-pyridinyl)-1-pyridine (TPP) were used as ligands to prepare a novel cobalt-based MOF (Co-MOF) which was used as a precursor to obtain five carbon-based materials at different temperatures (Co-C200/400/600/800/1000). Furthermore, five dyes were used as degradation targets to investigate the photocatalytic degradation performance of the title materials under UV light irradiation. Co-C1000 exhibited the best photocatalytic degradation performance for methyl orange (MO), and the degradation rate could reach 99.21%. The enhanced photocatalytic activity was attributed to narrower band-gaps and a synergistic effect originating from the well-aligned straddling band structures between Co/CoO/Co3O4 and C, also resulting in a faster interfacial charge transfer during the photocatalytic reaction. This study will aid in the development of photocatalysts generated from carbon-based materials via the pyrolysis transformation of MOFs, therefore greatly enhancing the photocatalytic performance. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) can be used as electrocatalysts for the CO2 reduction reaction (CO2RR) because of their well-dispersed metal centers. Silver is a common electrocatalyst for reduction of CO2 to CO. In this study, two Ag-MOFs with different structures of [Ag8O2(TIPE)6](NO3)4 (Ag-MOF1) and [Ag(TIPE)0.5CF3SO3] (Ag-MOF2) [TIPE = 1,1,2,2-tetrakis(4-(imidazol-1-yl)phenyl)ethene] were synthesized and used for CO2 electroreduction. The results show that Ag-MOF2 is superior to Ag-MOF1 and exhibits high CO faradaic efficiency (FE) of 92.21% with partial current density of 29.51 mA cm−2 at −0.98 V versus reversible hydrogen electrode (RHE). The FECO is higher than 80% in the potential range of −0.78 to −1.18 V. The difference may be caused by different framework structures leading to different electrochemical active surface areas and charge transfer kinetics. This study provides a new strategy for designing and constructing CO2 electroreduction catalysts and provides potential ways for solving environmental and energy problems caused by excessive CO2 emission. [ABSTRACT FROM AUTHOR]

Due to its large capacity and relatively high conductivity, cobalt sulfide has been considered an excellent electrode material for lithium-ion batteries, but its extreme volume change during charging and discharging and lower conductivity than graphite limits its development. In this work, composite nanosheets of MXene and N-doped carbon-confined cobalt sulfide nanosheets (CoS@NC/MXene) were synthesized by growing the Co metal–organic framework of ZIF-67 onto MXene sheets, followed by sulfidation treatment. Different from normal ZIF-67 generally prepared in methanol, this work fabricates ZIF-67 in aqueous solution, which induces ZIF-67 to undergo some degree of hydrolysis and form more dispersed Co layered hydroxides mounted onto MXene. Also, the MXene incorporation imparts better water stability to ZIF-67(Co) and helps maintain its morphology during the sulfidation. CoS@NC/MXene has a conductive network supported by MXene and enhanced by NC, as well as a 3D hierarchical porous structure offered by the rational combination of its components. These favorable characteristics allow CoS@NC/MXene to deliver a capacity of 691 mA h g−1 at 200 mA g−1 in the 100th cycle and retain the specific capacity of 382 mA h g−1 at a higher current density of 8000 mA g−1. [ABSTRACT FROM AUTHOR]

Rare-earth (RE) metal–organic frameworks (MOFs) offer unique optical, electronic, and magnetic properties. RE metals tend to make binuclear metal nodes resulting in dense nonporous coordination networks. Three dimensional porous RE-MOFs have been reported by preparing bigger metal nodes based on metal clusters often found as hexaclusters or nonaclusters. The formation of metal clusters (>2 metal ions) generally requires the use of fluorinated organic molecules reported as modulators. However, it was recently discovered that these molecules are not modulators, rather they act as reactants and leave fluorine in the metal clusters. The formation and types of fluorinated RE metal clusters have been discussed. These fluorinated clusters offer higher connectivity which results in porous MOFs. The presence of fluorine in these metal clusters offers unique properties, such as higher thermal stability and improved fluorescence. This frontier summarizes recent progress and gives future perspective on the fluorinated metal clusters in the RE-MOFs. [ABSTRACT FROM AUTHOR]

Among transition metals, cobalt ions exhibit superior catalytic activity in the peroxymonosulfate (PMS) degradation of pollutants. However, practical application is hindered by their high rate of ion leaching and the propensity for particle reunion issues. In this study, a novel cobalt metal–organic framework catalyst, denoted as CUST-565 ([Co3(BTB)2(BIPY)2]·4.5H2O·DMA), was synthesized via a one-step solvothermal method. The obtained crystal was employed as a catalyst to activate PMS for degrading two pollutants, methyl orange (MO) and rhodamine B (RhB), in wastewater. The catalyst demonstrated efficacy in PMS, achieving 97% degradation of MO and 98% degradation of RhB within 30 min at an initial concentration of 20.0 mg L−1. Additionally, various factors affecting dye degradation, including PMS dosage, catalyst dosage, temperature, initial pH, and coexisting anions, were investigated. Radical quenching experiments confirmed the presence of sulfate radicals (SO4˙−), hydroxyl radicals (HO˙), superoxide radicals (O2˙−), and singlet oxygen (1O2) in the system. After four cycles, CUST-565 retained its ability to catalytically degrade approximately 80% of the pollutants. These observed stability and reusability properties, corroborated by a series of characterization analyses before and after use, suggest that CUST-565 exhibits reliable performance. This work contributes to the development of cobalt-PMS catalysts for efficiently degrading dyes in wastewater. [ABSTRACT FROM AUTHOR]

Two new metal–organic frameworks (MOFs), namely, {[Zn(HL)(bpea)]·DMF}n (Zn-MOF-1) and {[Co(HL)(bpea)]·DMF}n (Co-MOF-2) (H3L = 3-(3,5-dicarboxybenzyloxy)benzoic acid, bpea = 1,2-di(pyridyl)ethane), were obtained by the reaction of H3L and N-containing ligand bpea with Zn(NO3)2·6H2O and Co(NO3)2·6H2O, respectively. The isomorphic Zn-MOF-1 and Co-MOF-2 featured a 3D penetrating framework with different stabilities, luminescence, and catalytic properties. Luminescence measurement indicated that Zn-MOF-1 could be used to detect Al3+ through a turn-on effect with a detection limit of 0.42 μM. The sensing mechanism experiments showed that the enhanced luminescence of Zn-MOF-1 toward Al3+ may be due to the weak interaction between Al3+ and Zn-MOF-1 and the absorbance-caused enhancement (ACE) mechanism. Meanwhile, both Zn-MOF-1 and Co-MOF-2 showed interesting CO2 adsorption properties and could catalyze the cycloaddition of CO2 to epoxides resulting in 96 and 92% ideal products within 12 hours, respectively. They can be cycled up to 5 times without significant loss of catalytic efficiency. [ABSTRACT FROM AUTHOR]