Nickel Metal Organic Framework Research Articles

Nickel metal-organic frameworks for visible-light CO2 reduction under mild reaction conditions.

Photochemical CO2 conversion into carbon fuel is a promising route to explore renewable energy and relieve climate change. However, it is still a key challenge to achieve high selectivity to CO and simultaneously achieve high conversion efficiency in photochemical CO2 reduction. Herein, we demonstrate the effect of Ni metal centers as catalytic active sites for the photocatalytic conversion of CO2 to CO by designing and constructing Ni metal-organic framework (Ni-MOF) materials. In pure CO2, Ni-MOF catalyst exhibits outstanding performance for visible-light-driven reductive CO2 deoxygenation with a high CO evolution rate of 19.13 μmol h-1 (per 1 mg of catalyst) and CO selectivity of 91.4%, which exceeds those of most reported systems. Upon using isostructural Co-MOF as the catalyst to replace Ni-MOF, a moderate performance towards CO2 photoreduction and low CO selectivity (40.1%) were observed, implying that the performance of CO2 photoreduction and CO selectivity are dependent on unsaturated metal centers.

Highly dispersed Rh prepared by the in-situ etching-growth strategy for energy-saving hydrogen evolution

BackgroundThe development of high-efficiency electrocatalysts that surpass Pt-based catalyst to achieve more efficient hydrogen evolution reactions (HER) is significant. MethodsHerein, we constructed a series of highly dispersed rhodium (Rh) catalysts anchored on the Ni-based layered double hydrotalcite, which were formed by the in-situ etching-growth of nickel-metal organic frameworks (Ni-MOFs). These electrocatalysts not only exhibit outstanding performance in HER, but also in urea oxidation reaction (UOR). Significant findingsThe nickel-aluminum layered double hydroxide anchored Rh (Rh-NiAl LDH/NF) has the best catalytic activity for HER. It only needs an overpotential of 14 mV to reach a current density of 10 mA cm−2 in 1.0 M KOH, which is in the top class of the currently reported HER catalysts. In addition, the catalyst Rh-NiFe LDH/NF has good catalytic performance for UOR, and it only needs an ultra-low potential of 1.30 V to reach 10 mA cm−2. Hence, we constructed an electrolytic cell with the two electrodes for the urea-assisted hydrogen production, which is an energy-saving protocol for HER. The current density of 50 mA cm−2 can be reached when the cell voltage is only 1.40 V, which is 150 mV less than the traditional water splitting to produce H2.

A new nickel metal organic framework (Ni-MOF) porous nanostructure as a potential novel electrochemical sensor for detecting glucose

A new nickel metal organic framework (Ni-MOF) porous nanostructure as a potential novel electrochemical sensor for detecting glucose

Electronic Modulation Caused by Interfacial Ni‐O‐M (M=Ru, Ir, Pd) Bonding for Accelerating Hydrogen Evolution Kinetics

AbstractDesigning definite metal‐support interfacial bond is an effective strategy for optimizing the intrinsic activity of noble metals, but rather challenging. Herein, a series of quantum‐sized metal nanoparticles (NPs) anchored on nickel metal–organic framework nanohybrids (M@Ni‐MOF, M=Ru, Ir, Pd) are rationally developed through a spontaneous redox strategy. The metal‐oxygen bonds between the NPs and Ni‐MOF guarantee structural stability and sufficient exposure of the surface active sites. More importantly, such precise interfacial feature can effectively modulate the electronic structure of hybrids through the charge transfer of the formed Ni‐O‐M bridge and then improves the reaction kinetics. As a result, the representative Ru@Ni‐MOF exhibits excellent hydrogen evolution reaction (HER) activity at all pH values, even superior to commercial Pt/C and recent noble‐metal catalysts. Theoretical calculations deepen the mechanism understanding of the superior HER performance of Ru@Ni‐MOF through the optimized adsorption free energies of water and hydrogen due to the interfacial‐bond‐induced electron redistribution.

Three dimension Ni/Co-decorated N-doped hierarchically porous carbon derived from metal-organic frameworks as trifunctional catalysts for Zn-air battery and microbial fuel cells

Development of noble metal-free catalysts with great electrocatalytic performance and stability is of importance for electrochemical energy conversion and storage devices. Herein, we reported the synthesis of trifunctional catalysts with three-dimension (3D) hierarchically porous nitrogen-doped carbon framework with Ni-Co dual metal-involving and carbon nanotubes growth derived from nickel metal-organic framework. The as-synthesized catalyst exhibited better oxygen reduction reaction performance under both neutral and basic conditions compared with commercial Pt/C catalysts. Under basic electrolyte, the oxygen evolution reaction performance of the synthesized catalyst was comparable to that of commercial IrO2 catalysts and reasonable hydrogen evolution activity was achieved compared with reported non-noble metal-based catalysts. The assembled microbial fuel cell using the as-prepared material as the air electrode exhibited a maximum power density of 1971.2 mW m−2 and could steadily operate for more than 250 h of feed period. Furthermore, the Zn-air battery fabricated with the obtained catalyst showed excellent power density and rechargeability, which were superior to that of a Zn-air battery using Pt/C/IrO2 as the air electrode. We anticipate that the results described here can provide a new idea for design of multifunctional electrocatalysts for energy conversion and storage devices.

High electromagnetic wave absorption and thermal management performance in 3D CNF@C-Ni/epoxy resin composites

Electronic packaging materials with efficient heat dissipation and anti-electromagnetic-interference performance are highly desirable to realize the long-term stable operation of highly integrated electronic devices. Such combined functions of heat dissipation and anti-electromagnetic-interference are achieved here by filling 3D CNF@C-Ni network skeleton in epoxy resins (EP). The CNF@C-Ni is a carbon nanofibers network skeleton embedded with micron flower-like C-Ni particles and has been obtained by carbonizing nickel metal–organic frameworks (Ni-MOF) embellished bacterial cellulose. The 3D CNF@C-Ni network skeleton provides a highly efficient heat transfer channel for EP, rendering a high thermal conductivity of 0.5 W·m−1K−1 at room temperature for the 5 wt% CNF@C-Ni filled EP, ~2.8 times higher than that of pristine EP. In addition, the flower-like C-Ni particles realize an optimization in the impedance matching of CNF@C-Ni/EP, enabling a high electromagnetic wave absorption performance in the wave-transparent epoxy resins. In particular, a lowest reflection loss value of −49.77 dB at 13.44 GHz with a maximum effective bandwidth of 5.44 GHz (from 12.08 to 17.52 GHz) has been achieved in the 5 wt% CNF@C-Ni filled epoxy resins with a thickness of 2.2 mm. Such a new dual-functionated epoxy resin with combined high electromagnetic wave absorption and thermal management performance shows great potential in manufacturing of highly integrated electronic devices.

Fishbone-like Ni3S2/Co3S4 integrated with nickel MOF nanosheets for hybrid supercapacitors

It is still a challenge to improve the electronic conductivity and expose more active sites of metal-organic frameworks (MOFs). Herein, the fishbone-like Ni3S2/Co3S4 grown on nickel foam (NCS/NF) was employed as a conductive support for in-situ growing nickel MOF (NiMOF) nanosheets to enhance their electrochemical properties. The as-prepared NiMOF@Ni3S2/Co3S4/NF (NiMOF@NCS/NF) exhibited a high areal specific capacity of 8.7C cm−2 at 1 mA cm−2, and the capacity retention remains 65% at 50 mA cm−2. Furthermore, the assembled NiMOF@NCS/NF//AC hybrid supercapacitor achieves an intriguing energy density of 58.8 Wh kg−1 at the power density of 781.3 W kg−1, and the capacity retention remains 96.2% after 10,000 charge/discharge cycles. The prominent electrochemical performance of NiMOF@NCS/NF can be ascribed to the remarkable electronic conductivity and specific capacity of Ni3S2/Co3S4 composites coupled with their three-dimensional porous structure.

Bimetallic Co0.4Ni1.6P derived from cobalt functionalized a new nickel metal-organic-framework as an advanced electrode for high-performance supercapacitors

A new nickel metal organic framework (MOF) based on 4-cyan-5-acidamide-bisimidazole were fabricated using hydrothermal method. The Co@Ni-MOFwasprepared by doping Ni-MOF with Co2+through post-synthetic modification method. The bimetallic Co0.4Ni1.6P was obtained through phosphorization of Co@Ni-MOF and showed high specific capacity 330F/g at 1 A/g and capacity retention was 96% over 5000 cycles. The supercapacitor device was prepared (Co0.4Ni1.6P//AC) and demonstrated specific energy of 30.9 Wh/kg at power of 806 W/kg. These results provided a new way to design bimetallic phosphide (MOF-based materials) for supercapacitor application.

Synthesis of nickel-metal organic framework nanoplates with pyridine modulation and application to supercapacitors

2D MOFs have been widely investigated for their improved of stability and capacitance. In this work, the two-dimensional (2D) nickel-metal organic frameworks (Ni-MOFs) were prepared by a one-pot hydrothermal reaction with the assistance of a modulator. To control the thickness and lateral dimensions at the same time, the Ni-MOF (NiBpy-Py) structure was produced through in-situ substitution by pyridine (py) in the synthesis. The prepared 2D Ni-MOF nanoplates, with a thickness of approximately 23 nm and a lateral dimension ranging from 250 nm to approximately 1 μm, have been demonstrated to be an ideal candidate for supercapacitors because of their high capacitance and well-designed chemical stability. The results of NiBpy-Py showed a high capacitance of 222.5 F g−1 at a constant current of 0.5 A g−1 in a three-electrode setup. Moreover, NiBpy-Py demonstrated a specific capacitance of 178.3 mF cm−2 in a two-electrode system. After 1000 charge-discharge cycles at a constant current of 2 A g−1, the capacitance was maintained at 128 F g−1. We believe that the synthetic method proposed in this work would contribute greatly to the further exploration of unique MOF nanostructures.

Flexible paper-based Ni-MOF composite/AuNPs/CNTs film electrode for HIV DNA detection

It is very important to develop a rapid, simple, low cost point-of-care (POC) method for the early diagnosis of pathogens. In this work, a flexible paper-based electrode based on nickel metal-organic framework (Ni-MOF) composite/Au nanoparticles/carbon nanotubes/polyvinyl alcohol (Ni–Au composite/CNT/PVA) was constructed to detect target human immunodeficiency virus (HIV) DNA by DNA hybridization using methylene blue (MB) as a redox indicator. The CNT/PVA and Ni–Au composite were deposited on the cellulose membrane by vacuum filtration and drop-coating method in turn to obtain Ni–Au composite/CNT/PVA (CCP) film electrode. Compared to the CNT/PVA film electrode, CCP film electrode makes a higher loading of the probe DNA for its large specific surface area and conjugated π-electron system that can provide hydrogen bond sources to achieve interactions between MOF and single-stranded DNA, which improves the sensitivity for detecting target DNA. The variation of peak current for MB molecules adsorbed onto DNA before and after hybridization with HIV DNA was monitored. Electrochemical results proved that the CCP film maintained stable electrochemical property even after bending 200 times or stretching under different strains from 0% to 20%. The flexible paper electrode showed excellent sensing performance with a linear range of 10 nM–1 μM and a low detection limit of 0.13 nM. The target HIV DNA was successfully detected even in complex serum samples using the flexible CCP film electrode. Therefore, the simple and inexpensive flexible paper-based MOF composite film electrode can also be utilized for other pathogens POC diagnosis.

2D ultrathin NiMOF decorated by Ti3C2 MXene for highly improved photocatalytic performance

Two-dimensional (2D) nanomaterials, especially 2D ultrathin layered nanomaterials, have been under increasing demand for solar energy usage and conversion owing to their unique characteristics such as large surface area, easily accessible catalytic sites and high electron transfer efficiency. In this work, layered Ti3C2 was used as the noble-metal-free cocatalyst to design 2D/2D composite by a simple electrostatic self-assembly process, which was based on the ultrathin nickel metal organic framework (UNiMOF) nanosheets. Thanks to the similar layered structures, a conductive and intimate interface formed between Ti3C2 and UNiMOF, which could promote the charge transfer and accelerate the separation of photoexcited electrons and holes. Thus, the obtained 2D/2D UNiMOF/Ti3C2 hybrids exhibited higher activity for photocatalytic degradation of methylene blue (MB) than bare UNiMOF under UV–vis light irradiation, and the activity was boosted by almost 4.0 times when loaded with 1.5 wt% Ti3C2. Moreover, the as-synthesized UNiMOF/Ti3C2 composites showed excellent stability. The possible mechanism for photocatalytic degradation of MB was also explored.

The sensing performance toward taxifolin and lithium storage property based on nickel-metal organic frameworks and carbon nanotubes composite

Nickel-based metal organic framework (Ni-MOF) and carbon nanotubes composite (Ni-MOF/CNTs) is constructed via in situ self-assembly of Ni-MOF in the presence of CNTs solution. The obtained electrode (Ni-MOF/CNTs) exhibits sensitive response toward the detection of taxifolin by significantly enhancing the redox peak currents and decreasing the peak-to-peak separation. Under the selected conditions, the peak current linearly relates with taxifolin concentration in the range of 4.0 × 10−8 ~ 1.0 × 10−5 mol L−1 with the detection limit of 1.33 × 10−8 mol L−1 (S/N = 3). Otherwise, the lithium storage results reveal that Ni-MOF/CNTs with enhanced conductivity exhibits benign cycling stability and rate capability, with coulomb efficiency around 100%. This Ni-MOF/CNTs electrode may lay the foundation for the Ni-MOF based materials in electrochemical application.

Enhanced electrochemical performances of activated carbon (AC)-nickel-metal organic framework (SIFSIX-3-Ni) composite and ion-gel electrolyte based supercapacitor

In this study, we investigated that the activated carbon (AC)-based supercapacitor and introduced SIFSIX-3-Ni as a porous conducting additive to increase its electrochemical performances of AC/SIFSIX-3-Ni composite-based supercapacitor. The AC/SIFSIX-3-Ni composites are coated onto the aluminum substrate using the doctor blade method and conducted an ion-gel electrolyte to produce a symmetrical supercapacitor. The electrochemical properties of the AC/SIFSIX-3-Ni composite-based supercapacitor are evaluated through cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge/discharge tests (GCD). The AC/SIFSIX-3-Ni composite-based supercapacitor showed reasonable capacitive behavior in various electrochemical measurements, including CV, EIS, and GCD. The highest specific capacitance of the AC/SIFSIX-3-Ni composite-based supercapacitor was 129 F g−1 at 20 mV s−1.

Removal of cadmium ions from aqueous solutions using nickel metal-organic framework: isotherm, kinetic studies, optimization, and modeling by response surface methodology (RSM)

Removal of cadmium ions from aqueous solutions using nickel metal-organic framework: isotherm, kinetic studies, optimization, and modeling by response surface methodology (RSM)

Lattice-matching Ni-based scaffold with a spongy cover for uniform electric field against lithium dendrites.

Herein, carbonized nickel metal organic framework scaffolds at nickel foam (CNS@NF) were fabricated to regulate Li-ion plating/stripping in lithium cells. CNS@NF would contribute to uniform Li nucleation and low overpotential due to the small lattice mismatch ratio and homogenous lithiophilic sites. Moreover, the spongy structure of the carbonized MOF can reduce the local current density by smoothening the sharp edges of NiO. Owing to these advantages, both the symmetric cells and full cells exhibited excellent electrochemical performance.

Green Synthesis of Nickel Borides Supported over Multiwall Carbon Nanotube As a Novel Catalyst for Hydrogen Evolution

The use of non-renewable fuels such as coal, oil, and natural gas significantly affects ecological system and human health. A substantial effort has been spending to find an eco-friendly and efficient energy source. Hydrogen appears as a green energy source which emits water as its byproduct during the combustion. The primary concern of hydrogen fuel is its dependence on fossil fuels in the production. Hydrogen feedstock material like Sodium borohydride (NaBH4) becomes potential, alternative source for manufacturing hydrogen fuel. However, the reaction between NaBH4 and water was slow and required a durable catalyst 1,2,3. The synthesis method of some catalysts is often expensive and require the use of various toxic chemicals4. The purpose of this study was to discover a green method of synthesizing nickel borides composite (NiB@MWCNT) and to utilize it in enhancing hydrogen generation reaction. The composite was synthesized from supported nickel metal organic framework (Ni-MOF-5) in the presence of Multiwalled Carbon Nanotube (MWCNT). The structure and composition of NiB@MWCNT was determined by Powder X-Ray Diffraction (PXRD), Scanning Electron Mircroscopy (SEM, Figure 1), Energy Dispersive X-Ray Spectroscopy (EDS), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). The catalytic efficiency of NiB@MWCNT was tested at temperatures of 281K, 295K, and 303K. The temperature trials indicated the activation energy was 43 kJ mol-1. NiB@MWCNT also showed a steady hydrogen generation of 44.4 ml through the reusable test.

Purified mesoporous nickel metal organic framework as electrocatalyst for hydrogen evolution reaction (HER) in basic medium

Metal organic framework or MOFs are found to be a good catalyst for hydrogen evolution in view of its excellent structural features like porous nature and well-defined morphology. This report describes the synthesis of Nickel-MOF prepared by solvothermal approach and further purified by a chemical process. Both impure and purified Nickel-MOFs are fabricated as electrodes for evaluating HER reaction. The performance towards electrocatalytic activity is affected due to the impurities present in the porous structure. In view of investigating the effect of activation/purification process towards morphology and in-turn HER activity, activation and purification is carried out to enhance the performance of MOFs. The electrochemical characterization proves high electrocatalytic activity for purified Ni-MOF with high rate kinetics towards HER than impure Ni-MOF. The Tafel slope of purified Nickel MOF is estimated to be 73.7 mV/dec with a low charge transfer resistance of 1.84 Ω, whereas the unpurified Ni-MOF shows 87.47 mV/dec and 3.85 Ω. Results show that pure Ni-MOF has abundant catalytic active edge sites and obeys Volmer-Heyrvosky mechanism with makes desorption of hydrogen as rate determining step.

0D/2D MXene Quantum Dot/Ni-MOF Ultrathin Nanosheets for Enhanced N2 Photoreduction

To improve the photocatalytic efficiency of the N₂ reduction reaction, MXene quantum dots (Ti₃C₂-QDs) and two-dimensional (2D) nickel metal–organic framework (Ni-MOF) with different ratios were fabricated by a simple self-assembly strategy to form type II heterojunctions. The resultant composites showed enhanced absorption and excellent interfacial charge-transfer capabilities according to the optical and photoelectron properties. The optimal Ti₃C₂-QD/Ni-MOF heterostructure exhibited a considerable ammonia yield rate (88.79 μmol gcₐₜ–¹ h–¹). By means of X-ray absorption near-edge fine structure (XANES) technique, it was found that the interaction of Ti₃C₂-QD and Ni-MOF could accelerate the electron transfer, and Ni site would be the main area to enrich the electron density as well as adsorb and activate N₂. Finally, with the aid of density functional theory (DFT) calculations and in situ Fourier transform infrared spectrometry (FTIR), the reaction pathway and intermediate products were studied.

Nickel metal–organic framework (Ni-MOF) derived NiO/C@CNF composite for the application of high performance self-standing supercapacitor electrode

Compared to conventional electrode, a self-standing structure electrode is an effective way to achieve high performance of supercapacitor by maximizing the use of active material. We present a new combination of nickel oxide–carbon composites fabricated by directly carbonizing a nickel metal–organic framework (Ni-MOF)@carbon nanofiber (CNF) for a self-standing electrode of the supercapacitor application. The new scheme utilizes the CNF film as a substrate with high electron transferring capability and as a backbone of a self-standing electrode as well. It is observed that the MOF-derived NiOs with a diameter of ~ 8 nm are uniformly distributed in the carbon matrix and result in the improvement of the electrical conductivity. The self-standing electrode, NiO/C@CNF composite, provides a high rate capability with high specific capacitances of 742.2 and 671.1F g−1 (at 1 and 10 A g−1), respectively. An asymmetric supercapacitor (ASC) constructed from the NiO/C@CNF and the activated carbon exhibits an excellent specific energy density of 58.43 Wh kg−1 at a power density of 1,947 W kg−1. It is also confirmed that the ASC shows a good cycle stability from the long-term cycling test. It is demonstrated that the proposed nickel oxide–carbon composite has a potential as promising self-standing electrode materials for supercapacitors.

Stretchable Electrochemical Biosensing Platform Based on Ni-MOF Composite/Au Nanoparticle-Coated Carbon Nanotubes for Real-Time Monitoring of Dopamine Released from Living Cells

Existing electrochemical biosensing platforms, using traditional rigid and unstretchable electrodes, cannot monitor the biological signaling molecules released by cells in a mechanically deformed state in real time. Here, a stretchable and flexible electrochemical sensor was developed based on nickel metal-organic framework composite/Au nanoparticle-coated carbon nanotubes (Ni-MOF composite/AuNPs/CNTs) for sensitive detection of dopamine (DA) released by C6 living cells in real time. A Ni-MOF composite was obtained by introducing Ni, NiO, and a carbon frame onto the surface of two-dimensional (2D) Ni-MOF nanosheets using an efficient one-step calcination method. The hybrid of Ni-MOF composite/AuNPs/CNTs that deposited on the poly(dimethylsiloxane) (PDMS) film endowed the sensor with excellent electrochemical performance with a wide linear range of 50 nM to 15 μM and a high sensitivity of 1250 mA/(cm2 M) and also provided the sensor with desirable stability against mechanical deformation. Furthermore, the stretchable electrode also displayed good cellular compatibility while C6 living cells can be cultured and proliferated on it with strong adhesion. Then, the DA released by C6 living cells with chemical induction in both natural and stretched states was monitored using our stretchable and flexible electrochemical sensor in real time. This indicates that our new design of flexible Ni-MOF composite/AuNPs/CNTs/PDMS (NACP) film electrodes provides more opportunities for the detection of chemical signals released from cells and soft living organisms even under mechanically deformed states.