Cobalt Metal-organic Framework Research Articles

CTAB-Co-MOFs@AuPt NPs as signal probes for the electrochemical detection of carcinoembryonic antigen 15-3.

A sensitive electrochemical strategy for carcinoembryonic antigen 15-3 (CA15-3) detection isreported using CTAB-Co-MOFs@AuPt NPs as signal probes. The electrochemical strategy was designed as follows: First, the graphene aerogel@gold nanoparticles (GA@Au NPs) nanocomposites were employed to modify the sensing surface for promoting electron transfer rate and primary antibody (Ab1) immobilization due to GA possesses a large specific surface area, eminent conductivity, and a 3D network structure. Cobalt metal-organic frameworks (CTAB-Co-MOFs) synthesized were then used as a carrier for AuPt NPs and secondary antibody (Ab2) immobilization (notes: labelled-Ab2). With sandwich immunoreaction, the labelled-Ab2 was captured on the surface of the GA@Au NPs nanocomposites. Finally, differential pulse voltammetry (DPV) was employed to register the electrochemical signal of the immunosensor at the potential of - 0.85V (vs SCE) in phosphate buffer saline (PBS) containing 2.5mM H2O2. It was verified that the electrochemical reduction signal from Co3+ to Co2+ was recorded. The AuPt NPs could catalyze the reaction of H2O2 oxidizing Co2+ to Co3+, resulting in the amplification of the electrochemical signal. Under the selected conditions, the immunosensor can detect CA15-3 in the range10 µU/mL to 250 U/mL with a low detection limit of 1.1 µU/mL. In the designed strategy, the CTAB-Co-MOFs were not only employed as carriers for AuPt NPs, but also acted as signal probes. The CTAB-Co-MOFs were investigated including SEM, TEM, XPS, and XRD. The applicationability of theimmunosensor was evaluated using serum sample, demonstrating the immunosensor can be applied to clinic serum analysis.

A facile strategy of designing a new crystalline cobalt metal–organic framework as a new efficient and robust heterogeneous catalyst for olefin oxidation reaction

A novel three-dimensional (3D) metal-organic compound Co3(BDC)3(DMF)2(H2O)4.2DMF (DMF= N,N-dimethylformamide; BDC= 1,4-benzenedicarboxylate) (Co-BDC (1)) has been synthesized under solvothermal method using Co2+ salt and BDC as a rigid ligand. The material was structurally characterized by single-crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR), thermogravimetric (TGA), inductively coupled plasma (ICP), and elemental (CHN) techniques. Oxidation of some olefins was evaluated with tert‑butyl hydroperoxide (TBHP) in acetonitrile in the presence of Co-BDC (2) (activated Co-BDC (1)) as a heterogeneous catalyst. Among the substrates used for the oxidation reaction, desirable conversions of 97 %, 81.6 %, and 76 % were obtained for cyclooctene, 1-hexene, and norbornene, respectively. Finally, the catalyst was recycled and reused (four times) without a remarkable decrease in the catalytic activity.

Fabrication of graphene-based magnetic carbon composites derived from iron cobalt metal-organic framework as dual-band electromagnetic wave absorbers

The fabrication of advanced magnetic carbon electromagnetic wave (EMW) absorbers derived from metal-organic framework (MOF) with thin thickness, wide bandwidth, strong absorption strength and low filling ratio remains a huge challenge. In this paper, CoFe2O4/CoFe/C/Graphene composites were prepared by a simple two-step way of solvothermal reaction and carbonization treatment. The results of micromorphology analysis revealed that as the carbonization temperature increased, the obtained carbon frameworks changed from a spindle shape to dodecahedron-like shape and finally to a tile shape, and the carbonization temperature had a notable influence on the electromagnetic parameters and EMW absorption properties of the magnetic carbon composites. It should be noted that the obtained CoFe2O4/CoFe/C/Graphene composites exhibited comprehensive excellent EMW absorption performance when the carbonization temperature was 750.0 ℃ and the filling radio was only 15.0 wt%, namely the effective absorption bandwidth reached up to 4.8 GHz and the optimal minimum reflection loss was −40.2 dB at a thickness of 2.06 mm. A distinct dual-band (C band and Ku band) absorption feature was observed when the thickness exceeded or equaled 4.5 mm. Furthermore, the underlying electromagnetic dissipation mechanisms were also elucidated. Therefore, our results could provide a valuable reference for preparing excellent magnetic carbon EMW absorbers derived from MOF.

Construction of MOFs derived porous carbon based core–shell hetero-structure electrode for superior asymmetric supercapacitor

The design of electrode materials with high performance is very important to improve the energy density of supercapacitors (SCs). The combination of electrical double layer capacitor and pseudo-capacitive materials can significantly improve the electrochemical performance of material, but reasonable structural design can inhibit the slow Faraday dynamic mismatch caused by different storage mechanisms. In this study, NiCoB nanosheets were grown on the surface of cobalt metal-organic frameworks (Co-MOF) derived porous carbon (Co-C) by chemical precipitation method to form a core–shell hetero-structure Co-C@NiCoB electrode. The Co-C@NiCoB electrode has the specific capacitance of 2990 F g−1 at 1 A g−1, which is significantly higher than that of Co-C (416 F g−1) and NiCoB (1052 F g−1). In order to further increase the energy density of the device, the carbon nano-sheets with cactus shape as cathode were obtained by calcination of Co-MOF (CNS). The asymmetric SCs with CNS as cathode and Co-C@NiCoB as anode have a high energy density of 66.03 Wh kg−1 at the power density of 763.35 W kg−1 and exceptional cycling life with capacitance retention of 92.1 % over 10,000 cycles.

Two-mode sensing strategies based on tunable cobalt metal organic framework active sites to detect Hg2+

Heavy metal pollution poses a major threat to human health, and developing a user-deliverable heavy metal detection strategy remains a major challenge. In this work, two-mode Hg2+ sensing platforms based on the tunable cobalt metal-organic framework (Co-MOF) active site strategy are constructed, including a colorimetric, and an electrochemical assay using a personal glucose meter (PGM) as the terminal device. Specifically, thymine (T), a single, adaptable nucleotide, is chosen to replace typical T-rich DNA aptamers. The catalytic sites of Co-MOF are tuned competitively by the specific binding of T-Hg2+-T, and different signal output platforms are developed based on the different enzyme-like activities of Co-MOF. DFT calculations are utilized to analyze the interaction mechanism between T and Co-MOF with defect structure. Notably, the two-mode sensing platforms exhibit outstanding detection performance, with LOD values as low as 0.5 nM (colorimetric) and 3.69 nM (PGM), respectively, superior to recently reported nanozyme-based Hg2+ sensors. In real samples of tap water and lake water, this approach demonstrates an effective recovery rate and outstanding selectivity. Surprisingly, the method is potentially versatile and, by exchanging out T-Hg2+-T, can also detect Ag+. This simple, portable, and user-friendly Hg2+ detection approach shows plenty of promise for application in the future.

Enhancing dye degradation using a novel cobalt metal-organic framework as a peroxymonosulfate activator.

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.

Template-Directed In-situ Grown Bimetallic Nanoarchitectures with Hydroxide Active Sites Enriched Multi-Charge Transfer Routes for Energy Storage

Cobalt metal-organic frameworks were used as templates to obtain densely stacked two-dimensional ultrathin nanosheets of nickel/cobalt metal-organic frameworks on carbon cloth via in situ deposition at room temperature. The freestanding...

Samarium-doped cobalt metal–organic framework as a versatile catalyst for the conversion of furfural and 2-methylfuran to high-value-added biofuel precursors

Fabrication of a samarium-doped cobalt metal–organic framework (Sm/Co-TTA MOF) for catalysing the conversion of furfural and 2-methylfuran to a biofuel precursor 5,5′-(furan-2-ylmethylene)bis(2-methylfuran) (FMBMF) via hydroxyalkylation-alkylation (HAA).

Nitrogen-rich cobalt metal–organic framework as a heterogeneous catalyst for the degradation of organic dye pollutants in water via peroxymonosulfate activation

A Co3-btca heterogeneous catalyst can activate PMS to efficiently degradate organic dyes rhodamine B and methyl violet in water.

Bioelectrocatalytic reduction by integrating pyrite assisted manganese cobalt-doped carbon nanofiber anode and bacteria for sustainable antimony catalytic removal

A novel manganese cobalt metal–organic framework based carbon nanofiber electrode (MnCo/CNF) was prepared and used as microbial fuel cell (MFC) anode. Pyrite was introduced into the anode chamber (MnCoPy_MFC). Synergistic function between pyrite and MnCo/CNF facilitated the pollutants removal and energy generation in MnCoPy_MFC. MnCoPy_MFC showed the highest chemical oxygen demand removal efficiency (82 ± 1%) and the highest coulombic efficiency (35 ± 1%). MnCoPy_MFC achieved both efficient electricity generation (maximum voltage: 658 mV; maximum power density: 3.2 W/m3) and total antimony (Sb) removal efficiency (99%). The application of MnCo/CNF significantly enhanced the biocatalytic efficiency of MnCoPy_MFC, attributed to its large surface area and abundant porous structure that provided ample attachment sites for electroactive microorganisms. This study revealed the synergistic interaction between pyrite and MnCo/CNF anode, which provided a new strategy for the application of composite anode MFC in heavy metal removal and energy recovery.

Controllable defect engineering based on cobalt metal-organic framework for boosting oxygen evolution reaction

Defect engineering on metal-organic frameworks (MOFs) provides high flexibility to rationally design advanced oxygen evolution reaction (OER) catalysts with low overpotential and high stability. However, fundamental understanding the effect of defect concentration on catalytic OER activity is still quite ambiguous. Herein, the Co-MOF-Dx catalysts with regulated oxygen defects concentration are deliberately constructed via coupling one-pot solvothermal synthesis with NaBH4 chemical reduction process. Experimental findings propose that the oxygen defect concentration within Co-MOF-Dx gradually increases with raising the NaBH4 content, which could provide a flexible platform to tailor the electronic structure around active Co site and optimize adsorption/desorption capacity of oxygen intermediates. When the introduction content of NaBH4 is up to 5 mg, the resulting abundant unsaturated coordination defects could endow the Co-MOF-D5 catalyst with optimized electronic structure and more exposed active sites for improving charge transfer and adsorption/desorption capacity. It is found that the optimized Co-MOF-D5 can drive the current density of 10 mA cm−2 only at a low overpotential of 300 mV with the small Tafel slope of 53.1 mV dec−1 in alkaline medium. This work sheds light on the way for the development of high-performance MOF catalysts via modulating defect concentration.

Facile synthesis of cobalt, nickel and manganese-based metal organic framework derived layered double hydroxides on Ni foam as effective binder-free electrodes of energy storage devices

Metal organic framework (MOF) derivatives have attracted intensive attention as the active material of energy storage devices. Layered double hydroxide (LDH) with large surface area, high redox capability and good cycling stability is regard as one of efficient active materials. Developing MOF-derived LDH with multiple metals can possibly achieve excellent surface properties, high electrical conductivity and abundant redox reactions. However, synthesizing MOF-derived LDH is time-consuming and requires high temperature environments. In this work, a simple and time-effective precipitation and etching process is proposed to synthesize MOF-derived LDH on nickel foam (NF) as binder-free electrodes of energy storage devices. The cobalt, nickel and manganese are utilized to design MOF-derived LDH with different metal species and numbers. The trimetallic MOF-derived LDH based on Co, Ni and Mn presents a high specific capacitance (CF) of 1113.7 F/g at 20 mV/s, due to abundant electroactive sites and multiple redox states for carrying out large numbers of redox reactions. The energy storage device composed of the trimetallic MOF-derived LDH and carbon on NF as electrodes presents the maximum energy density of 61.5 Wh/kg at the power density of 750 W/kg, and the CF retention of 92.5% and Coulombic efficiency of 95% after 10,000 charge/discharge cycles.

Sustainable Hierarchically Porous Reusable Metal–Organic Framework Sponge as a Heterogeneous Catalyst and Catalytic Filter for Degradation of Organic Dyes

Advanced oxidation processes based on sulfate radical are considered one of the most promising wastewater treatment technologies currently. Among heterogeneous catalysts, cobalt metal–organic framework (MOF) has been widely reported. However, the inherent powder form of MOF hinders its practical application and reusability. Therefore, innovative methods to increase the loading capacity and the accessibility of MOF active sites in monolithic materials are required. Therefore, a simple and scalable method of fabricating a stable, hierarchical porous zeolitic imidazolate framework (ZIF‐67) 3D sponge by growing MOF on a short electrospun fiber network is shown. The sponge can efficiently activate peroxymonosulfate and rapidly degrade an exemplary organic dye (Rhodamine B) with a degradation efficiency of 100%. The resulting multilevel, hierarchical porous structure is beneficial to the mass transfer of reagents making the catalytic process efficient. This also enables the use of the ZIF‐67 as an efficient catalytic filter for continuous removal of dye. The sponge can be recycled and reused for several cycles due to its robustness without loss in efficiency. The proposed research strategy provides a new way to design MOF 3D monolithic materials.

Enhanced cobalt MOF electrocatalyst for oxygen evolution reaction via morphology regulation

Developing productive and stable catalysts using common elements for the production of hydrogen via water splitting is highly desirable. Due to their well-designed composition, unique morphology, and highly crystalline structure, metal–organic frameworks (MOFs) exhibit good electrocatalytic performance and have attracted significant research interest as OER catalysts. The optimized Co-MOF-C catalyst reported herein exhibited a smaller overpotential at 10 mA cm−2 and Tafel slope (342 mV, 119 mV dec−1) than Co-MOF-A and Co-MOF-B in an alkaline solution for OER. Moreover, Co-MOF-C showed better long-term durability and stability with negligible deactivation compared with the other MOF catalysts. The apparent laminar nanomorphology of Co-MOF-C provided more accessible active metal centers, better electrical conductivity, and improved kinetics, explaining its better performance as an OER electrocatalyst.

A "Trinity" Design of Li-O2 Battery Engaging the Slow-Release Capsule of Redox Mediators.

Nonaqueous Li-O2 battery (LOB) represents one of the promising next-gen energy storage solutions owing to its ultrahigh energy density but suffers from problems such as high charging overpotential, slow redox kinetics and Li anode corrosion etc., calling for a systemic optimization of the battery configuration and structural components. Herein, an ingenious "trinity" design of LOB is initiated by implementing a hollowed cobalt metal organic framework (MOF) impregnating iodized polypyrrole simultaneously as the cathode catalyst, anode protection layer and slow-release capsule of redox mediators, so as to systemically address issues of impeded mass transport and redox kinetics on the cathode, dendrite growth and surface corrosion on the anode, as well as limited intermediate solubility in the low donor-number (DN) solvent. As a result of the systemic effort, the LOB constructed demonstrates an ultralow discharge/charge polarization of 0.2V, prolonged cycle life of 1200h and total discharge capacity of 28.41 mAh cm-2 . Mechanistic investigations attribute the superb LOB performance to the redox-mediated solution growth mechanism of crystalline Li2 O2 with both enhanced reaction kinetics and reversibility. This study offers a paradigm in designing smart materials to raise the performance bar of Li-O2 battery towards realistic applications. This article is protected by copyright. All rights reserved.

Synthesis, Structural Versatility, Magnetic Properties, and I- Adsorption in a Series of Cobalt(II) Metal-Organic Frameworks with a Charge-Neutral Aliphatic (O,O)-Donor Bridge.

Four new metal-organic frameworks based on cobalt(II) salts and 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide (odabco) were obtained. Their crystallographic formulae are [Co3(odabco)2(OAc)6] (1, OAc- = acetate), [Co(H2O)2(HCOO)2]·odabco (2), [Co2(H2O)(NO3)(odabco)5](NO3)3·3.65H2O (3), and [Co2(DMF)2(odabco)4](NO3)4·3H2O (4; DMF = N,N-dimethylformamide). Crystal structures of 1-4 were determined by single-crystal X-ray crystallography. Coordination polymer 1 comprises binuclear and mononuclear metal-acetate blocks alternating within uncharged one-dimensional chains, in which odabco acts as a bridging ligand. A layered Co(II) formate 2 contains odabco only as guest molecules located in the interlayer space. Layered compound 3 and three-dimensional 4 have cationic coordination frameworks with 26% and 34% specific void volumes, respectively, unveiling high structural diversity of Co(II)-odabco MOFs based on quite a rare aliphatic moiety. Magnetization measurements were performed for 1, 3, and 4 and the obtained data were interpreted on the basis of their crystal structures. A strong (J/kB~100 K) antiferromagnetic coupling was found within binuclear metal blocks in 1. Ion exchange experiments revealed a considerable iodide uptake by 3 resulting in an up to 75% guest nitrate substitution within the voids of a coordination framework, found by capillary zone electrophoresis data and confirmed by single-crystal XRD. A preservation of 3 crystallinity during the exchange allowed for the guest I- positions within a new adduct with the formula [Co2(H2O)(NO3)(odabco)5]I2(NO3)·1.85H2O (3-I) to be successfully determined and the odabco aliphatic core to be revealed as a main adsorption center for quite large and easily polarizable iodide anions. In summary, this work presents a comprehensive study for a series of 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide-based MOFs of cobalt(II) within the framework of magnetic properties and reports the first example of anion exchange in odabco-based coordination networks, supported by direct X-ray structural data. The reported results unveil promising applications of such frameworks bearing ligands with an aliphatic core in the diverse structural design of selective adsorbents and other types of functional materials.

A novel 3D cobalt-metal organic framework based mixed O/N-donor ligands: Synthesis, structure, and electrochemical OER performance

Cobalt metal organic frameworks (Co-MOFs), as promising potential electrocatalyst materials, have been extensively investigated owing to high catalytic active center, uniform catalytic site, large specific surface area, adjustable pore. A new Co-MOF, namely, {[Co2(L)(4,4′-bbibp)2]·4(H2O)}n [YMUN 9 (YMUN for Youjiang Medical University for Nationalities)], has been synthesized based on semi-rigid dicarboxylic acid and rigid imidazole ligands (H2L = 3,5-bis(3,5-dicarboxylphenoxy)benzoic acid, 4,4′-bbibp = 4,4′-bis(benzimidazol-1-yl)biphenyl). YMUN 9 displays a 3D framework through by means of single-crystal X-ray diffraction (SC-XRD). In order to present the structure more clearly, YMUN 9 can be defined as a 3D 2-nodal (4,4)-connected network with the point symbol of {4·85}2{42·104} through topology analysis. YMUN 9-D has been obtained based on YMUN 9 through a new strategy that of programmed heat treatment of YMUN 9. The oxygen evolution reaction (OER) electrochemical activity of YMUN 9-D has been investigated through cyclic voltammetry (CV), linear scanning voltammetry (LSV), chronopotentiometry (CP), and electrochemical impedance spectroscopy (EIS), in 0.1 M KOH electrolyte. The investigated results revealing that YMUN 9-D has a prominent overpotential of 273.9 mV (at J = 10 mA·cm−2), and keeps great chemical stability until 1000 mins. The Tafel slope of YMUN 9-D is 141.9 mV·dec−1 and its double layer capacitance is found to be 32 mF·cm−2. Compared to other MOFs materials, YMUN 9-D displays similar or superior electrocatalytic performance.

Supercapacitance of an integrated structure of nickel cobalt metal-organic framework decorated on electrospun functionalized carbon nanofiber

In order to enhance the electrochemical efficiency of supercapacitors, novel active electrode materials are being developed. This study provides a unique method to synthesize an integrated structure consisting of a nickel-cobalt metal-organic framework (NiCo-MOF) on functionalized carbon nanofiber (f-CNF) utilizing a single-step solvothermal method. Physicochemical characterization confirmed the successful synthesis of the integrated system of NiCo-MOF@f-CNF. This novel structure has the potential to significantly improve the electrochemical properties of the initially prepared material for use in supercapacitors. The synthesized electrode has a higher specific capacitance/capacity value of 788 F g−1 (315.2 C g−1) at 1 A g−1 and high cycling stability. The developed hybrid device exhibited a promising specific energy of 8.6 Wh kg−1 and a high specific power of 1147 W kg−1, demonstrating potential for practical applications. The current study suggests that the proposed material can be a viable electrode for high-efficiency supercapacitors.

Glucose oxidase-like Co-MOF nanozyme-catalyzed self-powered sensor for sensitive detection of trace atrazine in complex environments

The self-powered sensor (SPS) is a sensor method that does not require the external power source and has the potential for portable detection of environmental contaminants. In this work, for the first time, a biomolecule-free SPS for detection of ultra-trace triazine endocrine disruptor atrazine (ATZ) with high sensitivity and selectivity is constructed using a glucose oxidase (GOD)-like cobalt metal-organic framework (Co-MOF) nanozyme-modified high-performance anode and a molecularly imprinted cathode. By modulating the size and morphology of the prepared materials, Co-MOF nanozyme with superior GOD-like property (Michaelis constant Km = 15.8 mM) has been obtained and modified at the anode to catalyze glucose oxidation with high efficiency and provide energy continuously and stably for the SPS. The separation mode of anodic energy supply-cathodic recognition ensures the recognition effect without affecting the catalytic characteristic of Co-MOF and the output signal of the SPS. The designed SPS has a wide linear range of 1 pM–100 nM and a detection limit as low as 0.65 pM, as well as superior selectivity and good stability. The present work provides a promising approach for the design of self-powered sensors which can be extended to detection of a wider range of environmental pollutants.

Nickel–Cobalt Metal–Organic Framework CPO-27 and g-C3N4 for Oxygen Reduction Reaction in Alkaline-Exchange-Membrane Fuel Cell

Nickel–Cobalt Metal–Organic Framework CPO-27 and g-C₃N₄ for Oxygen Reduction Reaction in Alkaline-Exchange-Membrane Fuel Cell