Synthesis and Optimization of Ni-Based Nano Metal-Organic Frameworks as a Superior Electrode Material for Supercapacitor.

Metal-organic frameworks (MOFs) are hybrid materials that are being explored as active electrode materials in energy storage devices, such as rechargeable batteries and supercapacitors (SCs), due to their high surface area, controllable chemical composition, and periodic ordering. However, the facile and controlled synthesis of a pure MOF phase without impurities or without going through a complicated purification process (that also reduces the yield) are challenges that must be resolved for their potential industrial applications. Moreover, various oxide formations of the Ni during Ni-MOF synthesis also represent an issue that affects the purity and performance. To resolve these issues, we report the controlled synthesis of nickel-based metal-organic frameworks (NiMOFs) by optimizing different growth parameters during hydrothermal synthesis and by utilizing nickel chloride as metal salt and H2bdt as the organic ligand, in a ratio of 1:1 at 150 °C. Furthermore, the synthesis was optimized by introducing a magnetic stirring stage, and the reaction temperature varied across 100, 150, and 200 °C to achieve the optimized growth of the NiMOFs crystal. The rarely used H2bdt ligand for Ni-MOF synthesis and the introduction of the ultrasonication stage before putting it in the furnace led to the formation of a pure phase without impurities and oxide formation. The synthesized materials were further characterized by powder X-ray diffraction (XRD) technique, scanning electron microscopy (SEM), and UV-vis spectroscopy. The SEM images exhibited the formation of nano NiMOFs having a rectangular prism shape. The average size was 126.25 nm, 176.0 nm, and 268.4 nm for the samples (1:1)s synthesized at 100 °C, 150 °C, and 200 °C, respectively. The electrochemical performances were examined in a three-electrode configuration, in a wide potential window from -0.4 V to 0.55 V, and an electrolyte concentration of 2M KOH was maintained for each measurement. The charge-discharge galvanostatic measurement results in specific capacitances of 606.62 F/g, 307.33 F/g, and 287.42 F/g at a current density of 1 A/g for the synthesized materials at 100 °C, 150 °C, and 200 °C, respectively.

Facile Synthesis and Optimization of CrOOH/rGO-Based Electrode Material for a Highly Efficient Supercapacitor Device.

New electrode materials for supercapacitor devices are the primary focus of current research into energy-storage devices. Besides, exact control of the proportions of these new materials while forming electrodes for coin cell supercapacitor devices is very important for the large-scale manufacturing or at industrial scale. Here we report a facile synthesis of CrOOH with ascorbic acid and explore an exact composition with reduced graphene oxide to achieve a highly efficient electrode material for supercapacitor devices. The rGO is synthesized by modified Hummer's method followed by reduction with ascorbic acid, whereas ultrasmall CrOOH nanoparticles result via hydrothermal treatment of the reactants Cr(NO3)3, NaOH, and ascorbic acid at 120 °C for 12 h. The ultrasmall CrOOH nanoparticles show an amorphous phase with particle size range 3-10 nm and a calculated band gap of 3.28 eV. Six different composites are prepared by varying the proportion of CrOOH and rGO materials and further utilized as active electrode materials for fabrication of the coin cell supercapacitor devices. We report the highest specific capacitance for the 70% CrOOH and 30% rGO composite that exhibits a capacitance of 199.8 mF cm-2 with a long cyclic stability up to the tested 10,000 charge/discharge cycles. The proposed supercapacitor device exhibits a high energy and power density of 8.26 Wh kg-1 and 3756.9 W kg-1, respectively, at Ragone Plot, showing the commercial viability of the device.

Thermal and Rheological Characterization of Aqueous Nanofluids Based on Reduced Graphene Oxide (rGO) with Manganese Dioxide Nanocomposites (MnO2).

Nanofluids have become of interest in recent years thanks to their improved thermal properties, which make them especially interesting for microchannel heat sink applications. In this study, we prepared two aqueous nanofluids based on reduced graphene oxide (rGO) decorated with manganese dioxide (MnO2) at a concentration of 0.1 wt.%. The difference between the two nanofluids was in the preparation of the reduced graphene oxide decorated with MnO2. In the first case, the manganese salt was mixed with ascorbic acid before GO reduction with NaOH, and in the second case, the GO reduction with NaOH occurred under ascorbic acid. Ascorbic acid not only plays the role of a non-toxic and ecofriendly reducing agent but also acts as an important parameter to control the reaction kinetics. The structural, microstructural and spectral characterizations of the MnO2/rGO nanocomposite were conducted via X-ray diffractometry (XRD), Raman spectroscopy, FT-IR, TEM, SEM and EDS analyses. Moreover, the synthesized MnO2/rGO nanocomposites were utilized as nanofluids and their stability, thermal conductivity and rheological behaviors were studied. The thermal conductivity of the MnO2/rGO and MnO2AsA/rGO nanofluids was 17% and 14.8% higher than that of water for the average temperature range, respectively, but their viscosity remained statistically equal to that of water. Moreover, both nanofluids presented Newtonian behavior in the analyzed shear rate range. Therefore, both MnO2/rGO and MnO2AsA/rGO nanofluids are promising alternatives for use in applications with micro- and millichannel heat sinks.

Anisotropic Band-Edge Absorption of Millimeter-Sized Zn(3-ptz)2 Single-Crystal Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) have emerged as promising tailor-designed materials for developing next-generation solid-state devices with applications in linear and nonlinear coherent optics. However, the implementation of functional devices is challenged by the notoriously difficult process of growing large MOF single crystals of high optical quality. By controlling the solvothermal synthesis conditions, we succeeded in producing large individual single crystals of the noncentrosymmetric MOF Zn(3-ptz)2 (MIRO-101) with a deformed octahedron habit and surface areas of up to 37 mm2. We measured the UV-vis absorption spectrum of individual Zn(3-ptz)2 single crystals across different lateral incidence planes. Millimeter-sized single crystals have a band gap of E g = 3.32 eV and exhibit anisotropic absorption in the band-edge region near 350 nm, whereas polycrystalline samples are fully transparent in the same frequency range. Using solid-state density functional theory (DFT), the observed size dependence in the optical anisotropy is correlated with the preferred orientation adopted by pyridyl groups under conditions of slow crystal self-assembly. Our work thus paves the way for the development of optical polarization switches based on metal-organic frameworks.

Gold nanoparticle-decorated earth-abundant clay nanotubes as catalyst for the degradation of phenothiazine dyes and reduction of 4-(4-nitrophenyl)morpholine.

In the present work, halloysite nanotubes modified with gold nanoparticles (AuNPs-HNT) are successfully prepared by wet chemical method for the catalytic degradation of phenothiazine dyes (azure B (AZB) and toluidine blue O (TBO)) and also cleaner reduction of 4-(4-nitrophenyl)morpholine (4NM) in the sodium borohydride (NaBH4) media. The catalyst is formulated by modifying the HNT support with a 0.964% metal loading using the HNT supports modified with 3-aminopropyl-trimethoxysilane (APTMS) coupling agent to facilitate the anchoring sites to trap the AuNPs and to prevent their agglomeration/aggregation. The AuNPs-HNT catalyst is investigated for structural and morphological characterization to get insights about the formation of the catalyst for the effective catalytic reduction of dyes and 4NM. The microscopic studies demonstrate that AuNPs (2.75 nm) are decorated on the outer surface of HNT. The as-prepared AuNPs-HNT catalyst demonstrates AZB and TBO dye degradation efficiency up to 96% in 10 and 11 min, respectively, and catalytic reduction of 4NM to 4-morpholinoaniline (MAN) is achieved up to 97% in 11 min, in the presence of NaBH4 without the formation of any by-products. The pseudo-first-order rate constant (K1) value of the AuNPs-HNT catalyst for AZB, TBO, and 4NM were calculated to be 0.0078, 0.0055, and 0.0066 s-1, respectively. Moreover, the synthesized catalyst shows an excellent reusability with stable catalytic reduction for 7 successive cycles for both the dyes and 4NM. A plausible mechanism for the catalytic dye degradation and reduction of 4NM by AuNPs-HNT catalyst is proposed as well. The obtained results clearly indicate the potential of AuNPs-HNT as an efficient catalyst for the removal of dye contaminants from the aquatic environments and cleaner reduction of 4NM to MAN, insinuating future pharmaceutical applications.

Azide-Based High-Energy Metal-Organic Frameworks with Enhanced Thermal Stability.

We describe the structure and properties of [Zn(C6H4N5)N3] n , a new nonporous three-dimensional high-energy metal-organic framework (HE-MOF) with enhanced thermal stability. The compound is synthesized by the hydrothermal method with in situ ligand formation under controlled pH and characterized using single-crystal X-ray diffraction, elemental analysis, and Fourier transform infrared. The measured detonation temperature (T det = 345 °C) and heat of detonation (ΔH det = -0.380 kcal/g) compare well with commercial explosives and other nitrogen-rich HE-MOFs. The velocity and pressure of denotation are 5.96 km/s and 9.56 GPa, respectively. Differential scanning calorimetry analysis shows that the denotation of [Zn(C6H4N5)N3] n occurs via a complex temperature-dependent mechanism.

Graphene oxide: An efficient material and recent approach for biotechnological and biomedical applications.

The two-dimensional (2D) derivative of graphite termed graphene has widespread applications in various frontiers areas of nanoscience and nanotechnologies. Graphene in its oxidized form named as graphene oxide (GO) has a mixed structure equipped with various oxygen containing functional groups (epoxy, hydroxyl, carboxylic and carbonyl etc.) provides attachment sites to various biological molecules including protein, deoxyribonucleic acid (DNA), ribonucleic acid (RNA) etc. The attached biological molecules with the help of functional groups make it a promising candidate in research field of biotechnological and biomedical applications. The ease of processability and functionalization in aqueous solution due to available functional groups, amphiphilicity, better surface enhanced Raman scattering (SERS), fluorescence and its quenching ability better than graphene make GO a promising candidate for various biological applications. The amphipathetic nature and high surface area of the GO not only prepare it as a biocompatible, soft and flexible intra/inter cellular carrier but also provides long-term biocompatibility with very low cytotoxicity. Inspite of this, still we lack a very recent review for advanced biological applications of graphene oxide. This review deals the bio application of GO and the recent advancement as a biosensors, antibacterial agent, early detection of cancer, cancer cell imaging/mapping, targeted drug delivery and gene therapy etc.

pH-Controlled Assembly of 3D and 2D Zinc-Based Metal-Organic Frameworks with Tetrazole Ligands.

We report the synthesis and structural diversity of Zn(II) metal-organic framework (MOF) with in situ formation of tetrazole ligand 3-ptz [3-ptz = 5-(3-pyridyl)tetrazolate] as a function pH. By varying the initial reaction pH, we obtain high-quality crystals of the noncentrosymmetric three-dimensional MOF Zn(3-ptz)2 , mixed phases involving the zinc-aqua complex [Zn(H2O)4(3-ptz)2]·4H2O, and two-dimensional MOF crystals Zn(OH)(3-ptz) with a tunable microrod morphology, keeping reaction time, temperature, and metal-ligand molar ratio constant. Structures are characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-vis spectroscopy. We discuss the observed structural diversity in terms of the relative abundance of hydroxo-zinc species in solution for different values of pH.

Self-Assembled Hierarchical Formation of Conjugated 3D Cobalt Oxide Nanobead-CNT-Graphene Nanostructure Using Microwaves for High-Performance Supercapacitor Electrode.

Here we report the electrochemical performance of a interesting three-dimensional (3D) structures comprised of zero-dimensional (0D) cobalt oxide nanobeads, one-dimensional (1D) carbon nanotubes and two-dimensional (2D) graphene, stacked hierarchically. We have synthesized 3D self-assembled hierarchical nanostructure comprised of cobalt oxide nanobeads (Co-nb), carbon nanotubes (CNTs), and graphene nanosheets (GNSs) for high-performance supercapacitor electrode application. This 3D self-assembled hierarchical nanostructure Co3O4 nanobeads-CNTs-GNSs (3D:Co-nb@CG) is grown at a large scale (gram) through simple, facile, and ultrafast microwave irradiation (MWI). In 3D:Co-nb@CG nanostructure, Co3O4 nanobeads are attached to the CNT surfaces grown on GNSs. Our ultrafast, one-step approach not only renders simultaneous growth of cobalt oxide and CNTs on graphene nanosheets but also institutes the intrinsic dispersion of carbon nanotubes and cobalt oxide within a highly conductive scaffold. The 3D:Co-nb@CG electrode shows better electrochemical performance with a maximum specific capacitance of 600 F/g at the charge/discharge current density of 0.7A/g in KOH electrolyte, which is 1.56 times higher than that of Co3O4-decorated graphene (Co-np@G) nanostructure. This electrode also shows a long cyclic life, excellent rate capability, and high specific capacitance. It also shows high stability after few cycles (550 cycles) and exhibits high capacitance retention behavior. It was observed that the supercapacitor retained 94.5% of its initial capacitance even after 5000 cycles, indicating its excellent cyclic stability. The synergistic effect of the 3D:Co-nb@CG appears to contribute to the enhanced electrochemical performances.

Synthesis and optical properties of different CuO (ellipsoid, ribbon and sheet like) nanostructures.

We report the Synthesis of different CuO (ellipsoid, ribbon and sheet like) nanostructures in a solution phase with high yield at low cost bysimple reduction of aqueous solution of copper nitrate with alkaline solution of sodium hydroxide (NaOH). The morphology of the synthesized nanostructures is significantly influenced by the feedingconcentration of alkaline NaOH solution. Cu(OH)2 nanomaterials can be readily obtained by the reduction of Cu(NO3)2 solution with NaOH solution and these synthesized materials obtained atdifferent molar concentration of NaOH solution get transformed into different nanostructures ofCuO by subsequent heat treatment at 80 degrees C for half an hour. Nanoellipsoid, nanoribbon and nanosheet like structures were obtained after heating the copper nitrate solution reduced with 0.25 M, 0.50 M, 0.75 M and 1 M concentrated NaOH solution respectively. Optical absorption spectra and corresponding band gap calculation showed that these nanomaterials have higher band gap than their bulk materials.

Synthesis and characterization of different metal oxide nanostructures by simple electrolysis based oxidation of metals.

We report the Synthesis of different metal oxide (Cu2O, SnO2, Fe3O4 and PbO2) nanostructures by simple electrolysis based oxidation of metals (Cu, Sn, Fe and Pb). We have utilized the two electrode set up for the electrolysis and used different metal electrodes as anode and platinum as cathode. The synthesized nanomaterials were delaminated in the electrolyte. The microstructural characterization of synthesized materials in electrolytes after electrolysis at different electrode potentials revealed that the nanostructures strongly depend on the applied voltage between the electrodes. Various nanostructures (nanothreads, nanowires, nanocubes, nanotetrapods and hexagons-like) of metal oxides have been synthesized by this method. In case of copper electrode we have found nanothreads and nanowires of cuprous oxide. Tin electrode resulted nanothreads, nanotetrapod and nanocube like structures of tin oxide. Iron electrode resulted, nanowire like structures of iron oxide and lead sheet transformed into hexagon like and six petals like structures of lead oxide.

Lactose nano-probe optimized using response surface methodology.

A lactose nano-probe has been developed by immobilization of PsBGAL onto gold nanoparticles (AuNps). It is helpful for severe lactose intolerants for quality check of lactose hydrolyzed milk and estimation of hidden lactose present in variety of food products. Optimization of PsBGAL immobilization onto AuNps using spacer arm (cysteamine-glutaraldehyde) was carried out by response surface methodology (Box-Behnken design). The process has led to immobilization of enzyme onto AuNps with an efficiency of 140.81%. AuNp-PsBGAL was characterized using transmission electron microscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. Immobilized enzyme showed broad temperature and pH optima and a significant enhancement in catalytic efficiency (V(max)/K(m)) with respect to soluble PsBGAL. AuNp-PsBGAL was stable under dried conditions than wet conditions for 6 months with loss of 10.2% and 87.53%, respectively. It has reusability of over five batchwise uses, with almost no loss in activity. Hill's coefficient was found to be 1.71 corresponding to lactose concentration ranging from 0.1% to 2.0%.

Synthesis of copper nanoparticles by electrolysis of DNA utilizing copper as sacrificial anode.

Copper nanoparticles have been synthesized by anodic oxidation through a simple electrolysis process employing de-oxy ribonucleic acid (DNA) as electrolyte. Platinum was taken as cathode and copper as anode. The applied voltage was 4 V and the electrolysis was performed for duration of 1 h. The copper nanoparticles were prepared in situ from the electron beam irradiation on residues of electrolyte consisting of DNA and copper particles: DNA (Cu) complexes. The size of the nanoparticles ranges between 5-50 nm. A tentative explanation has been given for the formation of copper nanoparticles.