Nickel Metal Organic Framework Research Articles

Bimetallic Manganese–Nickel Metal–Organic Framework Anchored Hexyl-Aminated Carbon Nanotube Hybrid as an Anodic Material for Solid-State Asymmetric Supercapacitors

Bimetallic Manganese–Nickel Metal–Organic Framework Anchored Hexyl-Aminated Carbon Nanotube Hybrid as an Anodic Material for Solid-State Asymmetric Supercapacitors

Exploring the electrochemical synergy of metal sulfides and metal-organic framework composite as hybrid supercapacitor electrodes

Metal-organic frameworks (MOFs) are promising electrode materials however, they continue to seek improvements in both energy density and electrical conductivity. Within a wide array of available metal nodes and linkers, the task of refining and attaining a profound comprehension of charge storage mechanisms is still to accomplish. Herein nickel sulfide and nickel MOF were synthesized via hydrothermal method, their properties were investigated, and a binary composite was developed due to the high resistance of pristine MOFs. This composite demonstrated exceptional specific capacity of 787.8C/g at cost of 2.0A/g. To leverage real-world applications, a supercapattery was fabricated using the NiS/Ni-MOF as the positive electrode material and activated carbon as the negative electrode material. The device possesses maximum specific energy of 64.67Wh/kg and maximum specific power of 3200W/kg together with capacity retention of 91% after 5k charge-discharge cycles. To validate results, semi-empirical approach using Dunn’s model and power law is subjected to investigate the capacitive and diffusive contributions and b-values. This study shows that the binary composites of metallic sulfides with MOFs can possess potentials for their applications in real devices.

Flower-like 3D SnS decorated on nickel metal-organic framework for electrochemical detection of dimetridazole in food samples

Dimetridazole (DMZ) is a broad-spectrum antibiotic effective against bacterial and protozoan infections in humans and poultry farms. However, excessive DMZ intake leads to harmful effects. Thus, minimizing its environmental presence is crucial for sustaining daily life. This study presents an innovative approach to construct flower-like SnS particle decorations on a nickel metal-organic framework (Ni-MOF@SnS) as an electrocatalyst for DMZ detection. The Ni-MOF@SnS/GCE sensor exhibits exceptional electrocatalytic behavior, including a significantly reduced detection limit of 1.6 nM, extensive linear ranges from 0.01 μM to 60 μM and from 60 μM to 231 μM at lower and higher DMZ concentrations, respectively. It also shows enhanced sensitivity (0.139 μA μM−1 cm−2) and remarkable selectivity for DMZ detection using differential-pulse voltammetry (DPV). Furthermore, the proposed sensor demonstrates good recovery results with actual food samples.

Synthesis, characterization, crystal structures and photophysical properties of pillar-layer nickel metal-organic frameworks based on 2-aminoterepthalic acid and 5-aminoisopthalic acid

Five new compounds, [Ni2(2-NH2BDC)2(bipy)2(H2O)4](1), [Ni(5-aip)(phen)(H2O)3].2H2O (2), [Ni4(5-aip)3(bipy)3(H2O)7]. 19H2O (3), [Ni(5-aip)(bipy)(H2O)]n·2H2ODMF (4), and [Ni2(2-NH2BDC)2(phen)2(H2O)4](5) based on 5-aminoisophthalic acid and 2-aminoterepthalic acid, have been synthesized at room temperature using methanol and water solvent mixture and structurally determined using single crystal X-ray diffraction.Compounds 1–3 are discret complex while compound 4 shows two-dimensional (2D) pillar-layer architecture. In all these compounds, channels are observed through CH···O interactions between adjacent molecules. Compounds 1–5 displayed one broad emission band with a center at 384 nm when excited 294 nm in their solid state at room temperature, attributed to ligand-to-metal charge transfer. In comparison with emission peaks of 5-aminoisophthalic acid and 2-aminoterepthalic acid, the luminescent emissions of these compounds are blue-shifted due to a decrease of the energy gap between the ground and excited states in the ligand upon complexation with Ni(II).

Fe2O3 facilitating deeper transformation of Ni-MOF into active NiOOH for enhanced OER performance

Due to the large specific surface area and the highly-exposed active metal centers, nickel metal-organic frameworks (MOFs) have recently emerged as one of the excellent functional materials for oxygen evolution reactions (OER). Herein, we have construct uniformly distributed Fe2O3 particles within Ni-MOF nanosheets (Ni-MOF NSs) for enhanced OER performance. This electrocatalyst, prepared by a facile hydrothermal method, provides highly active Fe2O3 particles while preserving the framework structure of Ni-MOF for effective substrates diffusion. The optimal Fe2O3 doped Ni-MOF NSs deliver high stability in alkaline and exhibit striking OER performance with an overpotential of 232 mV at 10 mA cm−2 and a Tafel slope of 49.3 mV dec−1, outperforming the pristine Ni-MOF and most reported non-noble metal based electrocatalysts. The enhance catalytic activity of Fe2O3 doped Ni-MOF NSs is likely due to the introduction of Fe2O3 particles to facilitate the deeper transformation of Ni-MOF into active NiOOH species.

Pyrene Derivative Incorporated Ni MOF as an Enzyme Mimic for Noninvasive Salivary Glucose Detection Toward Diagnosis of Diabetes Mellitus.

Herein, we demonstrate the detection of glucose in a noninvasive and nonenzymatic manner by utilizing an extended gate field-effect transistor (EGFET) based on the organic molecule pyrene phosphonic acid (PyP4OH8) incorporated nickel metal-organic framework (NiOM-MOF). The prepared electrode responds selectively to glucose instead of sucrose, fructose, maltose, ascorbic acid, and uric acid in a 1× phosphate buffer saline solution. Also, utilizing the scanning Kelvin probe system, the sensing electrode's work function (Φ) is measured to validate the glucose-sensing mechanism. The sensitivity, detection range, response time, limit of detection, and limit of quantification of the electrode are determined to be 24.5 μA mM-1 cm-2, 20 μM to 10 mM, less than 5 s, 2.73 μM, and 8.27 μM, respectively. Most interestingly, the developed electrode follows the Michaelis-Menten kinetics, and the calculated rate constant (km) 0.07 mM indicates a higher affinity of NiOM-MOF toward glucose. The real-time analysis has revealed that the prepared electrode is sensitive to detect glucose in real human saliva, and it can be an alternative device for the noninvasive detection of glucose. Overall, the outcomes of the EGFET studies demonstrate that the prepared electrodes are well-suited for expeditious detection of glucose levels in saliva.

A four-fold interpenetrated MOF for efficient perrhenate/pertechnetate removal from alkaline nuclear effluents

The sequestration of 99Tc represents one of the most challenging tasks in nuclear waste decontamination. In the event of a radioactive waste leak, 99TcO4– (a main form of 99Tc) would spread into the groundwater, a scenario difficult to address with conventional anion exchange materials like resin and inorganic cationic sorbents. Herein, we present a nickel(II) metal-organic framework (MOF), TNU-143, featuring 3D four-fold interpenetrated networks. TNU-143 exhibits efficient ReO4– (a nonradioactive analogue of 99TcO4–) removal with fast anion exchange kinetics (<1 min), high sorption capacity (844 mg/g for ReO4–), and outstanding selectivity over common anions. More importantly, TNU-143 shows superior stability in alkaline solution and can remove 91.6% ReO4– from simulated alkaline high-level waste (HLW) streams with solid-liquid ratio of 40 g/L. The uptake mechanism is elucidated by the single-crystal structure of TNU-143(Re), showing that ReO4– anions are firmly coordinated to nickel cation to result in a 2D layered structures. Density functional theory (DFT) calculations confirm the transformation from TNU-143 to TNU-143(Re) is a thermodynamically favorable process. This work presents a new approach to the removal of ReO4–/99TcO4– from alkaline nulcear fuel using MOF sorbents.

Naphthalene Tetrazole-Based Nickel Metal-Organic Framework as a Filler of Polycarbonate Membranes to Improve CO2 and H2 Separation.

A tetrazole-naphthalene linker was used to prepare a nickel MOF (metal-organic framework) (NiNDTz) with interesting properties: a specific surface area SBET of 320 m2g-1 (SLangmuir 436 m2g-1), high thermal stability (Tdonset = 300 °C), and CO2 uptake of 1.85 mmolg-1, attributed to the tetrazole groups to be used as fillers in gas separation membranes. The role of these groups was crucial in the mechanical properties of mixed membranes prepared using polycarbonate as a polymer matrix, providing a very homogeneous filler distribution and also in the gas separation properties since a simultaneous increase in permeability and selectivity was achieved, especially in the hybrid membrane containing 20% filler (PC@NiNDTz-20%). This membrane exhibited an excellent balance between permeability (P) and selectivity (α) with an increase in the permeability of CO2 and H2, 177 and 185%, respectively, and improvements in the selectivity of these gases against greenhouse gases such as methane and ethylene (between 15 and 28% improvement). These results make this membrane competitive to deal with separations in which these gases are involved, and are of special interest for the H2/CH4 separation since it clearly improves the performance of pure PC and no better PC-based membranes have been reported in the literature for this separation.

Ru nanoparticles decorating ferrocene-based metal-organic framework for efficient and stable water-splitting electrocatalyst

The development of stable and efficient electrocatalysts based on metal-organic frameworks represents a main challenge for the overall water splitting process. Here, the ferrocene-based nickel metal-organic framework (NiFc-MOF) on nickel foam (NF) was synthesized using nickel chloride and 1, 1′-ferrocenedicarboxylic acid (FcDA) via a simple solvothermal method, and Ru nanoparticles (NPs) were reduced by FcDA and in situ grown on the surface of NiFc-MOF nanosheets. The as-prepared cactus-like Ru0.3@NiFc-MOF exhibits high electrocatalytic activity for hydrogen evolution reaction (HER) with a low overpotential of 25 mV@10 mA cm−2 and a Tafel slope of 45.05 mV dec−1. To reach a current density of 10 mA cm−2 for the oxygen evolution reaction (OER), a low overpotential of 210 mV was required. The assembled water electrolysis cell using Ru0.3@NiFc-MOF as bifunctional electrocatalysts only requires a voltage of 1.47 V to achieve a current density of 10 mA cm−2, indicating excellent electrolytic water splitting performance. In addition, the electrocatalytic activity of Ru0.3@NiFc-MOF's can keep the stability for 120 h Ru0.3@NiFc-MOF exhibits exceptional electrocatalytic performance, which can be attributed to both the intrinsic activity of Ru sites and the multiple active sites of NiFc-MOF.

Enhanced Electrochemical Hydrogenation of Benzaldehyde to Benzyl Alcohol on Pd@Ni-MOF by Modifying the Adsorption Configuration.

Electrocatalytic hydrogenation (ECH) approaches under ambient temperature and pressure offer significant potential advantages over thermal hydrogenation processes but require highly active and efficient hydrogenation electrocatalysts. The performance of such hydrogenation electrocatalysts strongly depends not only on the active phase but also on the architecture and surface chemistry of the support material. Herein, Pd nanoparticles supported on a nickel metal-organic framework (MOF), Ni-MOF-74, are prepared, and their activity toward the ECH of benzaldehyde (BZH) in a 3 M acetate (pH 5.2) aqueous electrolyte is explored. An outstanding ECH rate up to 283 μmol cm-2 h-1 with a Faradaic efficiency (FE) of 76% is reached. Besides, higher FEs of up to 96% are achieved using a step-function voltage. Materials Studio and density functional theory calculations show these outstanding performances to be associated with the Ni-MOF support that promotes H-bond formation, facilitates water desorption, and induces favorable tilted BZH adsorption on the surface of the Pd nanoparticles. In this configuration, BZH is bonded to the Pd surface by the carbonyl group rather than through the aromatic ring, thus reducing the energy barriers of the elemental reaction steps and increasing the overall reaction efficiency.

A doubly interpenetrated 3D nickel metal-organic framework for selective and sensitive turn-on sensing Hg2+ ions in water

Developing efficient fluorescent sensors for Hg2+ ions is significant due to the highly toxic and hazardous nature of Hg2+. Therefore, a novel nickel-metal framework [Ni-(Bibt)2-(ttpda)0.5] based on hybrid ligands 4,7-bis(1H-imidazol-1-yl)benzo[c][1,2,5]thiadiazole (Bibt) and 5,5′-(1,3,6,8-Tetraoxo-1,3,6,8-tetrahydrobenzo[lmn]-3,8-phenanthroline-2,7-diyl)diisophthalic acid (H4ttpda), briefly named as NiBT, was constructed, which exhibited a doubly interpenetrated 4, 6-connected fsc 3D network and a simplified topological symbol of {44∙610∙8}{44∙62}. In addition, NiBT showed high solvent and thermal stability, and pH durability (2.0 - 12.0). Moreover, NiBT could be used as a sensor for mercury ions in water with several favorable features including turn-on fluorescence changes, rapid response (within 30 s), high selectivity and sensitivity (LOD: 8.7 nM), broad pH response scope (4.0 - 11.0), and reusability (5 times). The sensing mechanism could be mainly attributed to the interactions between the Hg2+ and Bibt ligand by coordination with N atoms in the frameworks.

Ultrasensitive detection of ornidazole–antibiotic drug residues in water using NiMOFs functionalized MWCNT modified electrode

Nitroimidazole-based drugs are widely used as an antibiotic for the treatment of anaerobic bacterial and parasite illnesses. The widespread use of these drugs in animal feed and the consequent environmental pollution have become significant concerns in recent years. Simple, sensitive, and rapid detection of the antibody in various real samples is demanding research interest. Herein, we report a Nickel-metal organic framework functionalized Multiwalled Carbon nanotubes modified glassy carbon electrode (MWCNT@NiMOFs) as an ultrasensitive and rapid voltammetric sensor for the detection of ornidazole (ORDZ) in a neutral pH solution. The MWCNT@NiMOFs were prepared using a microwave-assisted solvothermal technique accompanied by an ultrasonication method. The designed MWCNT@NiMOFs offered a low charge transfer resistance (Rct) of 141 Ω along with excellent electrocatalytic activity, and high current density at the lowered cathodic peak potential (-0.62 V vs Ag/AgCl) for ORDZ detection. The surface adsorption capacity (Γs) in terms of surface excess and heterogeneous charge transfer rate constant (k0) of the MWCNT@NiMOFs were calculated to be 3.29 × 10-9 mol cm−2 and 5.33 × 10-3 cm s−1, respectively. Under an optimal working condition, differential pulse voltammetry measurements of ORDZ have shown concentration linearity in a window, 100 nm to 10 µM range with excellent sensitivity, 5.69 × 10-5A µM−1 cm−2, and detection limit, 26 nM (3.3/s). The designed MWCNT@NiMOFs offered appreciable reproducibility, and repeatability up to 30 days of storage time. The real-time quantitative evaluation of ORDZ in human urine and tap water specimens was done along with ∼ 100 % recovery values. Since the new approach is simple, selective, and separation-free, it can be extendable to a variety of real-time practical applications.

Nanosheet like Ni-MOFs/MWCNTs Composite Synthesis: Application to Trace Level Dopamine Measurement

Nanosheet like nickel metal organic frameworks (Ni-MOFs) have been synthesized using solvothermal route at room temperature. Functionalized multiwalled carbon nanotubes (MWCNTs) have been embedded into these MOFs through equilibration to prepare the composite. The composite (Ni-MOFs/MWCNTs) has been used as a modifier in sensor fabrication on glassy carbon electrode surface and successfully applied in dopamine measurement through cyclic voltammetry and square wave voltammetry techniques. The composite has exhibited enhanced electrochemical performance with a very low detection limit of 0.017 μM. The protocol showed wide linearity in the concentration range 2–200 μM with a sensitivity of 17.14 μAμM−1cm−2. The proposed electrochemical platform exhibited high sensitivity and selectivity in dopamine sensing which has been successfully applied to real sample matrices like human blood serum and injection.

In situ growth of a redox-active metal-organic framework on electrospun carbon nanofibers as a free-standing electrode for flexible energy storage devices.

The rational construction of free-standing and flexible electrodes for application in electrochemical energy storage devices and next-generation supercapacitors is an emerging research focus. Herein, we prepared a redox-active ferrocene dicarboxylic acid (Fc)-based nickel metal-organic framework (MOF) on electrospun carbon nanofibers (NiFc-MOF@CNFs) via an in situ approach. This in situ approach avoided the aggregation of the MOF. The NiFc-MOF@CNF flexible electrode showed a high redox-active behavior owing to the presence of ferrocene and flexible carbon nanofibers, which led to unique properties, including high flexibility and lightweight. Furthermore, the prepared electrode was utilized in a supercapacitors (SC) without the use of any binder, which achieved a specific capacity of 460 C g-1 at 1 A g-1 with an excellent cyclic retention of 82.2% after 25 000 cycles and a good rate capability. A flexible asymmetric supercapacitor device was assembled, which delivered a high energy density of 56.25 W h kg-1 and a long-lasting cycling performance. Also, the prepared electrode could be used as a freestanding electrode in flexible devices at different bending angles. The obtained cyclic voltammetry curves showed negligible changes, indicating the high stability and good flexibility of the electrode. Thus, the use of the in situ strategy can lead to the uniform growth of redox-active MOFs or other porous materials on CNFs.

Highly sensitive detection of kaempferol using electrochemical sensors based on 3D-ordered mesh interconnect C60-GO, Ni-MOF, and β-cyclodextrin

Kaempferol (KA), which is a biologically active natural polyphenol compound with considerable medicinal value, can be used to fight various diseases. Herein, a β-cyclodextrin/fullerene-graphene oxide/Nickel-metal–organic framework (β-CD/C60-GO/Ni-MOF) composite-based electrochemical sensor was developed to detect KA; the composite was characterized using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron (XPS) spectroscopy. The biocompatibility and host–guest recognition performance of β-cyclodextrin (β-CD); the porosity and the catalytic performance of the nickel-metal–organic framework (Ni-MOF); and the excellent electrical conductivity of fullerene-graphene oxide (C60-GO) work together to considerably improve the detection performance of the sensor for KA. The sensor has an extensive linear range (0.5–50 μM) and a low detection limit (58 nM) with an electrochemically active specific surface area of 0.0971 cm2; furthermore, the redox mechanism of KA in the sensor is explained. For the detection of actual natural samples of broccoli containing KA, satisfactory recovery rates and accuracy were observed; the recovery rate was 96.4 %–101.1 %.

Redox Additive Electrolyte Study of Metal-Organic Framework Derived Nickel Phosphide/Carbon Composite for Supercapacitors

The performance and operation of an energy storage device are significantly influenced by the electrolyte and electrode materials. Therefore, it is crucial to create an electrode material with a rational design and ensure that it is compatible with the electrolyte. In this study, we prepare nickel phosphides/carbon (NP@C) nanostructure from Nickel metal-organic framework (Ni-MOF) using one-step phosphidation technique for supercapacitor applications. This method aims to produce a distinctive structure with more redox-active sites as well as improved conductivity and a high-polarized surface that will speed up ion migration between the electrolyte and the surface. In order to further enhance the redox additive sites and thus the charge transport, we have employed redox additive electrolyte (0.2M K3[Fe(CN)6] in 1M Na2SO4). Using three electrode electrochemical system, NP@C electrode obtained a phenomenal specific capacitance of 2136.3 F/g at 3A/g with a specific capacitance retention rate of 90.6% after 5000 cycles. Furthermore, a symmetric supercapacitor device is assembled using two NP@C electrodes and redox additive electrolyte that renders a high energy density of 52.5 Wh/kg at a power density of 750 W/kg along with a long cycle life of ~93% after 10000 cycles. Hence, this study demonstrates how NP@C and redox additive electrolyte work in perfect harmony to generate a high-performance supercapacitor.

Solvent-Assisted Morphology-Induced Nickel Metal–Organic Framework as a Highly Efficient Electrode for Energy Storage Application

Solvent-Assisted Morphology-Induced Nickel Metal–Organic Framework as a Highly Efficient Electrode for Energy Storage Application

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.

Preparation of Mg-Mg2Ni/C composite and its excellent hydrogen storage properties

Magnesium hydride (MgH2) is a promising hydrogen storage material with high weight and volume hydrogen capacity. However, higher operating temperature and reversible hydrogen capacity decay inhibit its wide application. To address these issues, Mg-Mg2Ni/C was obtained by ball milling magnesium and nickel-Metal Organic Framework (Ni-MOF), and following calcinations. Initial dehydrogenation temperature of the composite is 530 K, 70 K lower than that of MgH2, and the apparent activation energy of the composite is 77.6 ± 2.1 kJ/mol, which is only 50% of MgH2. At 423 K, the hydrogen capacity of the composite is about 6 wt% within 3600 s, and keeps unchanged after ten cycles. The carbon material introduced by Ni-MOF inhibits the agglomeration of Mg, and Mg2Ni/Mg2NiH4 acts as a “hydrogen pump” in de/hydrogenation process. The carbon coating and “hydrogen pump” lead to the improvement of the ab/desorption kinetics and cycling stability. This attempt paves a potential way to achieve high performance Mg-based composite hydrogen storage materials.

Construction of Hydration Layer for Proton Transport by Implanting the Hydrophilic Center Ag0 in Nickel Metal-Organic Frameworks.

The directional arrangement of H2O molecules can effectively regulate the ordered protons transfer to improve transport efficiency, which can be controlled by the interaction between materials and H2O. Herein, a strategy to build a stable hydration layer in metal-organic framework (MOF) platforms, in which hydrophilic centers that can manipulate H2O molecules are implanted into MOF cavities is presented. The rigid grid-Ni-MOF is selected as the supporting material due to the uniformly distributed cavities and rigid structures. The Ag0 possesses potential combination ability with the hydrophilic substances, so it is introduced into the MOF as hydration layer centers. Relying on the strong interaction between Ag0 and H2O, the H2O molecules can rearrange around Ag0 in the cavity, which is intuitively verified by DFT calculation and molecular dynamics simulation. The establishment of a hydration layer in Ag@Ni-MOF regulates the chemical properties of the material and gives the material excellent proton conduction performance, with a proton conductivity of 4.86×10-2 Scm-1.