ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
In the present study, we report on the successful synthesis of hollow iron oxide nanospheres. The hollow Fe3O4 nanospheres were synthesized following a four-step procedure: electrospraying spherical PVP particles, coating these particles with alumina (Al2O3) and hematite (Fe2O3) through atomic layer deposition and, finally, a thermal reduction process to degrade the polymer (PVP) and convert hematite (Fe2O3) into magnetite (Fe3O4). A structural analysis using X-ray diffraction (XRD) confirmed the effectiveness of the thermal reduction process. A morphological analysis confirmed that the four-step procedure allowed for the obtainment of hollow iron oxide nanospheres, even though the reduction process caused a contraction in the diameter of the particles of almost 300 nm, but did not affect the thickness of the walls of the hollow spheres that remained at approximately 15 nm. Magnetic properties of the hollow iron oxide nanospheres enable their use in applications where the agglomeration of magnetic nanostructures in liquid media is commonly not allowed, such as in drug encapsulation and delivery.
ABSTRACT
The solvothermal synthesis of metal-organic frameworks (MOFs) often proceeds through competing crystallization pathways, and only partial control over the crystal nucleation and growth rates is possible. It challenges the use of MOFs as functional devices in free-space optics, where bulk single crystals of millimeter dimensions and high optical quality are needed. We develop a synthetic protocol to control the solvothermal growth of the MOF [Zn(3-ptz)2] n (MIRO-101), to obtain large single crystals with projected surface areas of up to 25 mm2 in 24 h, in a single reaction with in situ ligand formation. No additional cooling and growth steps are necessary. We propose a viable reaction mechanism for the formation of MIRO-101 crystals under acidic conditions, by isolating intermediate crystal structures that directly connect with the target MOF and reversibly interconverting between them. We also study the nucleation and growth kinetics of MIRO-101 using ex situ crystal image analysis. The synthesis parameters that control the size and morphology of our target MOF crystal are discussed. Our work deepens our understanding of MOF growth processes in solution and demonstrates the possibility of building MOF-based devices for future applications in optics.
