Nickel Metal Organic Framework Research Articles

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.

Improving oxygen reduction reaction by cobalt iron-layered double hydroxide layer on nickel-metal organic framework as cathode catalyst in microbial fuel cell

Cobalt Iron -layered double hydroxide (CoFe-LDH) nano sheets were attached to Nickel-metal organic frameworks (Ni-MOF) by utilizing hydrothermal reaction method, and CoFe-LDH@Ni-MOF was synthesized and worked as the cathode catalyst in microbial fuel cell. The surface of this composite material provided generous electrochemical active sites, consisting of wrinkled strips of CoFe-LDH adhering to a lamellar structure of Ni-MOF. In terms of the maximum output power density, CoFe-LDH@Ni-MOF as the catalyst was 211 mW/m2, 2.54 times higher than that of Ni-MOF (83 mW/m2), and it was stable at about 225 mV for 150 h. CoFe-LDH@Ni-MOF showed high oxygen reduction reaction capability and high specific surface area, and the electron transfer rate was accelerated. This work might set the stage for the development and utilization of fuel cell cathode catalysts.

A bifunctional luminescence sensor for biomarkers detection in serum and urine based on chemorobust Nickel(II) metal-organic framework

The rapid detection of biomarkers in bodily fluids is vital for clinical diagnosis and regular disease monitoring. In this work, a mixed-ligand strategy was employed to successfully construct a nickel(II) metal–organic framework ([Ni(H2TPTC)(bib)(H2O)2]n, NiMOF). Outstanding thermal and chemical stabilities coupled with the favorable luminescent performances endow NiMOF significant potential as an ideal bifunctional luminescence sensor with high selectivity and sensitivity, exceptional anti-interferences and recyclable performances, as well as low LODs for detecting 3-NT biomarker through “turn-off” luminescence quenching effects and HA biomarker through “turn-on” luminescence enhancement effects. Furthermore, such developed sensor was employed to quantify 3-NT biomarker in serum samples and HA biomarker in urine samples withsatisfactory results. In addition, the possible sensing mechanisms of NiMOF towards HA and 3-NT were also proposed. This work indicates the great potentials of MOFs-based biomarkers chemosensors.

Unveiling a cutting-edge bi-ligand nickel metal-organic framework as an electrode material for symmetric supercapacitors

Perylene diimide (PDI)-based MOFs feature a substantial specific capacitance, terrific cycle durability, swift charge/discharge rates, exceptional chemical as well as thermal endurance, diversity in electrode design, and inexpensive production costs. In light of these benefits, PDI-based MOFs are intriguing options for utilization in energy storage. Inspired by the distinctive features of perylene diimide-based ligands, highly conjugated and nitrogen-rich organic ligands Perylene diimide-L-dopa (PDI-L-Dopa) were incorporated to create the Ni-MOF architecture. The resulting hierarchical flower-like microspheres of bi-ligand Ni-MOF had better electron transport, conductivity, and wettability. When applied as electrode material in a three-electrode system considering a specific capacitance of 198 F/g at a current density of 1 A/g, the Ni-MOF-24 h electrode showcased beneficial electrochemical efficiency. XRD, FT-IR, and XPS were used to validate the formation of Ni-MOF and disclose the exact chemical composition and valence state inside the material. The hierarchical flower-like microsphere structure of the Ni-MOF, formed of 2D petal-like nanosheets, was revealed by FE-SEM and TEM. Additionally, when Ni-MOF-24 h electrodes used to fabricate symmetric supercapacitor (SSC), it reveals a high energy density (Ed) of 23 Wh/kg at a corresponding power density (Pd) of 600 W/kg along with extraordinary cyclic stability over 10,000 charge/discharge cycles with retaining 99 % of the initial capacitance. This research sheds light on the design and manufacture of innovative materials for long-term and efficient energy storage devices based on MOFs.

Two-Fold Interpenetrated Binuclear Nickel Metal-Organic Framework as a Heterogeneous Catalyst for N-Heterocycle Synthesis.

A binuclear Ni(II)-based metal-organic framework {[Ni2(btb)1.333(H2O)3.578(py)1.422]·(DMF)(H2O)3.25}n (Nibtb) was solvothermally synthesized (H3btb = 1,3,5-tri(4-carboxylphenyl)benzene, py = pyridine, DMF = N,N-dimethylformamide). Nibtb shows a rare 2-fold interpenetrating (3,4)-connected 3D network with a point symbol of (83)4(86)3 based on binuclear Ni(II) clusters. Nibtb as a heterogeneous catalyst combines the high stability of MOFs and excellent catalytic activity of nickel, which exhibits excellent catalytic activity for the synthesis of benzimidazoles and pyrazoles under mild conditions. Moreover, the catalyst can be easily separated and reused for seven successive cycles and maintains high catalytic activity.

Oxygen-doped NiCoP derived from Ni-MOFs for high performance asymmetric supercapacitor.

Oxygen doping strategy is one of the most effective methods to improve the electrochemical properties of nickel-cobalt phosphide (NiCoP)-based capacitors by adjusting its inherent electronic structure. In this paper, O-doped NiCoP microspheres derived from porous nanostructured nickel metal-organic frameworks (Ni-MOFs) were constructed through solvothermal method followed by phosphorization treatment. The O-doping concentration has a siginificant influence on the rate performance and cycle stability. The optimized O-doped NiCoP electrode material shows a specific capacitance of 632.4 F-g-1at 1 A-g-1and a high retention rate of 56.9% at 20 A g-1. The corresponding NiCoP-based asymmetric supercapacitor exhibits a high energy density of 30.1 Wh kg-1when the power density is 800.9 W kg-1, and can still maintain 82.1% of the initial capacity after 10 000 cycles at 5 A g-1.

Ni-Metal organic framework nanosheets and Ni3C/biomass porous carbon composite based long cycle life asymmetric supercapacitor

Asymmetric supercapacitors (ASCs), with their exceptional energy density and wider potential window while ensuring optimum power density, have gained substantial interest. Here, we introduce an ASC using Nickel-Metal Organic Framework (Ni-MOF) synthesized via On-pot solvothermal process as positive electrode and a hydrothermally grown composite encompassing Nickel-MXene with biowaste-derived brinjal carbon (MXAC) as negative electrode. The morphological analysis reveals the nanosheet-like morphology of Ni-MOF, whereas MXAC has a porous carbon skeleton bonded with MXene. In three-electrode configuration Ni-MOF shows specific capacitance of 536 F/g at 1 A/g at 0 to 0.4 V, while MXAC has 298 F/g at -1 to 0 V with 2M KOH. Further, the Ni-MOF//MXAC ASC device demonstrates specific capacitance of 146 F/g at 1 A/g with 1.5 V in 2M KOH, owing to the synergistic combination of Ni-MOF nanosheets with porous MXAC. Additionally, it provides 45.6 Wh/kg of energy density at power density of 750 W/kg and 85% capacitance retention after 10,000 cycles, signifying excellent stability.

Fabrication of graphite nanosheets decorated with Ni-MOFs for high performance supercapacitor electrode materials

Metal-organic frameworks (MOFs) with a periodic network structure are formed by self-assembled coordination links between one or more metal centers and organic ligands. In recent years, MOFs as electrode materials for supercapacitors (SCs) have been favored by researchers due to the tunable pore sizes, high surface area, and abundant active sites. However, the disadvantages of MOFs such as poor electrical conductivity and electrochemical stability limit their further application. In this work, nickel MOFs (Ni-MOFs) were grown in situ on graphite nanosheets (GNS) to form GNS decorated with Ni-MOFs (Ni-MOFs/GNS) by one-pot solvothermal method. The electrochemical properties of the Ni-MOFs/GNS as electrode materials could be tuned by adjusting the amount of GNS and the experimental conditions to regulate the structures. Moreover, Ni-MOFs grown in situ in GNS could improve the conductivity and dispersion of Ni-MOFs to avoid aggregation. The results indicated that the specific capacity of the Ni-MOFs/GNS electrode materials obtained at the optimal experimental conditions was 737.0C g−1 at 1 A g−1, and the capacity retention rate reached 61.1 % after 10,000 cycles. The power density was 424.0 W kg−1 at an energy density of 30.0 Wh kg−1. The fabrication strategy of the Ni-MOFs/GNS can be extended to synthesize other functional materials.

Aptamer tuned nanozyme activity of nickel-metal–organic framework for sensitive electrochemical aptasensing of tetracycline residue

It is urgently needed to develop high-performance method for tetracycline (TC) analysis to meet the growing concerns about food safety. Herein, a MOF of Ni2+-2,3,6,7,10,11-hexahydroxytriphenylene (Ni-HHTP) with peroxidase activity has been prepared and coated on a screen printing electrode, followed by non-covalent adsorption of tetracycline aptamer (TC-Apt) through the π-stacking. The spectroscopic and electrochemical assays show that TC-Apt can effectively enhance the nanozyme activity of Ni-HHTP using 3,3′,5,5′-tetramethylbenzidine (TMB)/H2O2 as the probe. Upon binding with TC, the configuration of TC-Apt is changed and desorbs from the Ni-HHTP, resulting in the decrease of the nanozyme activity of aptasensor. Based on this principle, the target TC can be analyzed in concentrations ranging from 10 pM to 1.0 μM, with a detection limit of 1.9 pM. The aptsensor is also applicable for TC analysis in fresh Ctenopharyngodon idella meat and milk, which provides a new approach for TC residue monitoring in food.

A multifunctional photoelectrochemical biosensing platform based on CdS QDs@TiO2-sensitizing Ni-TBAPy-SC coupled with multiple amplification for detection of HBV and thrombin

A multifunctional photoelectrochemical (PEC) biosensor using CdS quantum dots (QDs)-sensitized nickel-metal organic frameworks (MOFs) coupled with multiple amplification techniques was developed for detection of hepatitis B virus (HBV) and thrombin (TB). The tetra (p-benzoate) pyrene (TBAPy)Ni-SC was firstly modified on the electrode and showed an ultra-stable anodic photocurrent with excellent reproducibility. Subsequently AgInS2 QDs were attached to the electrode to much decrease the background signal and improved the assay sensitivity. Moreover, an effective PEC sensitizing probe was specifically designed by connecting a large number of CdS QDs onto TiO2 nanoparticles (NPs). After HBV target induced cyclic amplification to produce abundant output DNA, the CdS QDs@TiO2 signal probes were attached to the electrode by DNA hybridization, which turned the PEC signal of Ni-TBAPy-SC “on”, thus achieving sensitive detection of HBV. In addition, the CdS QDs@TiO2 nano-signal probe is released while target thrombin specifically binds to its aptamer, turning the PEC signal of Ni-TBAPy-SC “off” for thrombin detection. This work has developed a novel QD-sensitized Ni-TBAPy-SC PEC biosensor, which is able to rapidly detect dual targets and avoid false results, showing important value for early diagnosis of diseases.

Free-standing conductive nickel metal-organic framework nanowires as bifunctional electrodes for wearable pressure sensors and Ni-Zn batteries

Free-standing metal-organic frameworks (MOFs) with controllable structure and good stability are emerging as promising materials for applications in flexible pressure sensors and energy-storage devices. However, the inherent low electrical conductivity of MOF-based materials requires complex preparation processes that involve high-temperature carbonization. This work presents a simple method to grow conductive nickel MOF nanowire arrays on carbon cloth (Ni-CAT@CC) and use Ni-CAT@CC as the functional electrodes for flexible piezoresistive sensor. The resulting sensor is able to monitor human activity, including elbow bending, knee bending, and wrist bending. Besides, the soft-packaged aqueous Ni-Zn battery is assembled with Ni-CAT@CC, a piece of glass microfiber filters, and Zn foil acting as cathode, separator, and anode, respectively. The Ni-Zn battery can be used as a power source for finger pressure monitoring. This work demonstrates free-standing MOF-based nanowires as bifunctional fabric electrodes for wearable electronics.

Solvothermal synthesis of binder free Ni-MOF thin films for supercapacitor electrodes

To meet the energy demands of many sectors, energy storage systems must have high capacity, long cycling life, excellent energy density, and fast charge discharge rates. Because of their higher power and energy densities compared to other energy storage technologies, supercapacitors have been extensively researched in recent years. In this study, we synthesized binder-free thin films of the Nickel-Metal Organic Frameworks (Ni-MOFs) deposited on stainless steel substrate by using a simple solvothermal method. The Ni-MOF electrodes were systematically studied for their structural, morphological, and electrochemical characterizations. The microstructure of Ni-MOF electrodes varies with reaction concentration (from 0.1 mM to 0.4 mM) at the constant reaction temperature. X-ray diffraction (XRD) study reveals a crystallite phase of Ni-MOF material with a P-1 space group. The FESEM analysis shows a nanosheet-like structure of Ni-MOF material. The Ni-MOF electrode (0.3 mmol concentration) shows the specific capacitance of 850.42 F/g at a current density 1 mA/cm2 with a maximum energy density of 18.66 Wh/kg and power density of 1671 W/kg. These excellent electrochemical results demonstrate the potential of Ni-MOF for supercapacitor applications and provide directions for the development of future high-performance supercapacitor materials.

Two new metal-organic frameworks based on nitrogen-containing rigid tetracarboxylic acid ligand: Synthesis, crystal structure, characterization and DFT study

Two nickel metal-organic frameworks (Ni-MOFs) based on a nitrogen-containing rigid tetracarboxylic acid ligand had been synthesized by the hydrothermal method, namely {[Ni(H4L1)0.5(4,4′-bibp) (H2O)]·1.5H2O}n (1) and {[Ni(H4L1)(H2O)2]·H2O}n (2) (H4L1 = 5,5′-(1H-1,2,4-triazole-3,5-diyl)diisophthalic acid, 4,4′-bibp = 4,4′-di (1H-imidazol-1-yl)-1,1′-biphenyl). Crystal structure analysis revealed that the two complexes exhibited varied structures in the presence or absence of the auxiliary N-donor ligand 4,4′-bibp: the complex 1 was a three-dimensional (3D) metal-organic framework with a (1,2,4,5)-connected {4.64.8}2{42.64}3{6}2 topology. In the complex 2, the carboxylate ligand was used as a junction point to form a 2D layered structure with Ni(II). The results showed that the addition of the 4,4′-bibp has a very important effect on the structure of the complexes. Some conventional characterizations were carried out, such as: Infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric (TGA) analyses. Moreover, the ORCA program was used to perform density functional theory (DFT) calculations to investigate the molecular properties of the two complexes.

A novel flower-like nickel-metal-organic framework (Ni-MOF) membrane for efficient multi-component pollutants removal by gravity

The recycling of wastewater containing multiple pollutants is an urgent issue that requires sustainable and effective solutions. Gravity-driven membrane separation is a highly promising technology due to its low energy consumption, low transmembrane pressure, and ease of operation. To further enhance its advantages, this work explores the use of metal-organic frameworks (MOFs) for membrane modifications, which possess a porous structure, stable chemical properties, and high specific surface area. Specifically, flower-like nickel-based MOF particles were synthesized and assembled on a nylon membrane to prepare a novel Ni-MOF membrane. The Ni-MOF membrane displayed superhydrophilic properties, as evidenced by a water contact angle of 0°, and underwater superoleophobic properties, with an underwater oil contact angle of 154.37°. The Ni-MOF membrane demonstrated a significantly improved rejection rate for four types of dye solutions, particularly Congo red solution, which was rejected at a rate of 97.71% only through gravity-driven separation. Additionally, the Ni-MOF membrane exhibited exceptional performance for oil-water emulsion and microplastic wastewater, which was evidenced by the rejection of 95% and 99%, respectively. Moreover, the cycling tests revealed that the Ni-MOF membrane equipped long-term stability. These data demonstrated the Ni-MOF membrane had broad application prospects in the separation of wastewater containing multi-component pollutants.

Ni-MOF-based electrodes: A promising strategy for efficient overall water splitting

Hydrogen is a promising energy source to replace fossil fuels. Among the methods of generating hydrogen, electrochemical water splitting is distinguished by its ecologically friendly, high efficiency, sustainability, and ability to produce this element without the limitation of geological conditions and scaling devices. However, electrochemical water splitting is thermodynamically unfavorable, especially because its oxidation half-reaction (OER) and commercially available catalysts are expensive and not abundant in natural resources. The efficacy of commonly employed HER catalysts, such as Pt/C, is well-established. However, their high cost and limited natural resources present significant impediments. Given the slow kinetics of OER and the requisite catalyst demand for both HER and OER, it is paramount to pursue alternative solutions that are cost-effective, facile, and more widely accessible. Various new technologies and active materials have recently been developed in electrochemical water splitting for hydrogen production. There are still many knowledge gaps, including how preparation methods, chemical composition, and morphology of electrocatalysts affect both half-reactions of water splitting. Therefore, this work presents a smart approach to selectively activate NiMOF-based active materials in HER and OER. We demonstrate high-performance electrocatalysts based on Nickel/metal-organic frameworks (NiMOF) fabricated via two routes: A - drop cast on pristine Nickel foam with improved activity in OER (flower-like structure), B - Ni foam in situ impregnated by NiMOF during synthesis with improved activity in HER (rectangular-like structure). It allows the demonstration of highly efficient and robust electrocatalysts. Furthermore, in-situ studies on structural changes in the active materials have been conducted to reveal water-splitting half-reaction mechanisms.