Ready-to-use binder-free Co(OH)2 plates@porous rGO layers/Ni foam electrode for high-performance supercapacitors.

In this work, an outstanding nano-structured composite electrode is fabricated through the co-deposition of Co(OH)2 nanoplates and porous reduced GO (p-rGO) nanosheets onto Ni foam (NF). Through field emission scanning electron microscopy and transmission electron microscopy observations, it was confirmed that porous reduced graphene oxide sheets are completely wrapped by uniform hexagonal Co(OH)2 plates. Due to the unique architecture of both components of the prepared composite, a high surface area of 234.7 m2 g-1 and mean pore size of 3.65 nm were observed for the Co(OH)2@p-rGO composite. The constructed Co(OH)2@p-rGO/NF composite electrode shows higher energy storage capability compared to that of Co(OH)2/NF and p-rGO/NF electrodes. The Co(OH)2/NF electrode shows specific capacitances of 902 and 311 F g-1 at 5 and 30 A g-1, while the Co(OH)2@p-rGO/NF electrode delivers 1688 and 1355 F g-1 under the same current loads, respectively. Furthermore, when the current load was increased from 1 to 30 A g-1, 74.5% capacitance retention was observed for the Co(OH)2@p-rGO/NF electrode, indicating its outstanding high-power capability, while the Co(OH)2/NF electrode retained only 38.5% of its initial capacitance. The fabricated Co(OH)2@p-rGO/NF//rGO/NF ASC device shows an areal capacitance of 3.29 F cm-2, cycling retention of 91.2% after 4500 cycles at 5 A g-1 and energy density of 68.7 W h kg-1 at a power density of 895 W kg-1. The results of electrochemical tests prove that Co(OH)2@p-rGO/NF exhibits good performance as a positive electrode for use in an asymmetric supercapacitor device. The prepared porous composite electrode is thus a promising candidate for use in supercapacitor applications.

Bi Metal-Organic Framework (Ce/Ni-BTC) as Heterogeneous Catalyst for the Green Synthesis of Substituted Chromeno[4, 3-b]quinolone under Solvent Free Condition.

AIMS: Novel bi metal organic framework (b-MOF) is synthesized and used as a heterogeneous catalyst for the synthesis of chromeno[4, 3-b]quinolone derivatives via one-pot and solvent-free, four-component reaction of dimedone, aromatic aldehydes, 4-hydroxycoumarin and ammonium acetate at 110°C. BACKGROUND: b-MOFs can be used as a heterogeneous catalyst in the synthesis of many organic compounds. The active and multi-purpose sites in b-MOFs provide a varied function in their catalytic applications. In this paper, reductive CES method is applied for the synthesis of Ce0.47/Ni0.53-BTC b-MOF. The resulting b-MOF was used as a heterogeneous catalyst for the synthesis of chromeno[4, 3-b]quinolone via one-pot and solvent-free, fourcomponent reaction of dimedone, aromatic aldehyde, 4-hydroxycoumarin and ammonium acetate at 110 °C. METHOD: Ce0.47/Ni0.53-BTC was synthesized in an electrochemical cell composed of a stainless steel foil with a size of 5cm×5cm centered between two 5cm×5cm sized graphite plates as the anodes by the cathodic current density of 0.2 A/dm2 and placed in a solution of cerium nitrate (0.3 g), nickel nitrate (0.3 g), H3BTC (0.2 g) and NaNO3 (0.1 g) in ethanol (500 mL). Ce0.47/Ni0.53-BTC (10 mg) was added to a mixture of dimedone (1 mmol), aromatic aldehyde (1 mmol), hydroxycoumarin (1 mmol) and ammonium acetate (1.5 mmol) and stirred at 110 °C under solvent-free conditions for 45 min. The reaction evolution was controlled by the TLC (hexane:ethyl acetate, 4:1). Then, boiling ethanol was added to the reaction mixture and stirred at room temperature for 15 min. After the reaction completion, the catalyst was separated by centrifuge. Finally, the reaction mixture was placed in an ice bath, which resulted in a white solid product and recrystallized from ethanol to give the pure product. RESULT: The b-MOF catalyst showed very good efficiency in the synthesis of the desired compounds and can be easily recovered by centrifuge and reused at least five times without a decrease in catalytic activity. CONCLUSION: In this report, a novel bi metal-organic framework (Ce0.47/Ni0.53-BTC) is synthesized via the cathodic electrosynthesis method. The synthesized b-MOF is fully characterized by several characterization methods. The catalytic activity of Ce0.47/Ni0.53-BTC is investigated in the synthesis of chromeno[4, 3-b]quinolone derivatives via one-pot four-component reaction of dimedone, aromatic aldehyde, 4-hydroxycoumarin and ammonium acetate. The reaction optimization results showed that the highest isolated yield was obtained when the reaction was performed in solvent-free conditions at 110 °C. The catalyst showed to be highly efficient in the synthesis of the desired compounds and performing the reaction utilizing various starting materials gave the products in good isolated yields, which proves the generality and the scope of the method. The catalyst could easily be recovered by centrifuge and reused at least five times without a decrease in catalytic activity.

Bulk-Surface Modification of Nanoparticles for Developing Highly-Crosslinked Polymer Nanocomposites.

Surface modification of nanoparticles with functional molecules has become a routine method to compensate for diffusion-controlled crosslinking of thermoset polymer composites at late stages of crosslinking, while bulk modification has not carefully been discussed. In this work, a highly-crosslinked model polymer nanocomposite based on epoxy and surface-bulk functionalized magnetic nanoparticles (MNPs) was developed. MNPs were synthesized electrochemically, and then polyethylene glycol (PEG) surface-functionalized (PEG-MNPs) and PEG-functionalized cobalt-doped (Co-PEG-MNPs) particles were developed and used in nanocomposite preparation. Various analyses including field-emission scanning electron microscopy, Fourier-transform infrared spectrophotometry (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and vibrating sample magnetometry (VSM) were employed in characterization of surface and bulk of PEG-MNPs and Co-PEG-MNPs. Epoxy nanocomposites including the aforementioned MNPs were prepared and analyzed by nonisothermal differential scanning calorimetry (DSC) to study their curing potential in epoxy/amine system. Analyses based on Cure Index revealed that incorporation of 0.1 wt.% of Co-PEG-MNPs into epoxy led to Excellent cure at all heating rates, which uncovered the assistance of bulk modification of nanoparticles to the crosslinking of model epoxy nanocomposites. Isoconversional methods revealed higher activation energy for the completely crosslinked epoxy/Co-PEG-MNPs nanocomposite compared to the neat epoxy. The kinetic model based on isoconversional methods was verified by the experimental rate of cure reaction.

Kinetics of Cross-Linking Reaction of Epoxy Resin with Hydroxyapatite-Functionalized Layered Double Hydroxides.

The cure kinetics analysis of thermoset polymer composites gives useful information about their properties. In this work, two types of layered double hydroxide (LDH) consisting of Mg2+ and Zn2+ as divalent metal ions and CO32- as an anion intercalating agent were synthesized and functionalized with hydroxyapatite (HA) to make a potential thermal resistant nanocomposite. The curing potential of the synthesized nanoplatelets in the epoxy resin was then studied, both qualitatively and quantitatively, in terms of the Cure Index as well as using isoconversional methods, working on the basis of nonisothermal differential scanning calorimetry (DSC) data. Fourier transform infrared spectroscopy (FTIR) was used along with X-ray diffraction (XRD) and thermogravimetric analysis (TGA) to characterize the obtained LDH structures. The FTIR band at 3542 cm-1 corresponded to the O-H stretching vibration of the interlayer water molecules, while the weak band observed at 1640 cm-1 was attributed to the bending vibration of the H-O of the interlayer water. The characteristic band of carbonated hydroxyapatite was observed at 1456 cm-1. In the XRD patterns, the well-defined (00l) reflections, i.e., (003), (006), and (110), supported LDH basal reflections. Nanocomposites prepared at 0.1 wt % were examined for curing potential by the Cure Index as a qualitative criterion that elucidated a Poor cure state for epoxy/LDH nanocomposites. Moreover, the curing kinetics parameters including the activation energy (Eα), reaction order, and the frequency factor were computed using the Friedman and Kissinger-Akahira-Sunose (KAS) isoconversional methods. The evolution of Eα confirmed the inhibitory role of the LDH in the crosslinking reactions. The average value of Eα for the neat epoxy was 54.37 kJ/mol based on the KAS method, whereas the average values were 59.94 and 59.05 kJ/mol for the epoxy containing Zn-Al-CO3-HA and Mg Zn-Al-CO3-HA, respectively. Overall, it was concluded that the developed LDH structures hindered the epoxy curing reactions.

Investigation of intermolecular hydrogen bond interactions in crystalline L-cysteine by DFT calculations of the oxygen-17, nitrogen-14, and hydrogen-2 EFG tensors and AIM analysis.

A systematic computational study is carried out to investigate hydrogen bond (HB) interactions in the real crystalline structures of L-cysteine at 30 and 298 K by density functional theory (DFT) calculations of electric field gradient (EFG) tensors at the sites of O-17, N-14, and H-2 nuclei. One-molecule (monomer) and nine-molecule (cluster) models of L-cysteine are created by available crystal coordinates at both temperatures and the EFG tensors are calculated for both models to indicate the effect of HB interactions on the tensors. The calculated EFG tensors at the level of B3LYP and B3PW91 DFT methods and 6-311++G** and cc-pVTZ basis sets are converted to those experimentally measurable nuclear quadrupole resonance (NQR) parameters i.e. quadrupole coupling constants (qcc) and asymmetry parameters (eta(Q)). The evaluated NQR parameters reveal that the EFG tensors of (17)O, (14)N, and (2)H are influenced and show particular trends from monomer to the target molecule in the cluster due to the contribution of target molecule to classic N-H...O, and non-classic S-H...O and S-H...S types of HB interactions. On the other hand, atoms in molecules (AIM) analyses confirm the presence of HB interactions and rationalize the observed EFG trends. The results indicate different contribution of various nuclei to HB interactions in the cluster where O2 and N1 have major contributions. The EFG tensors as well as AIM analysis at the H6 site show that the N1-H6...O2 HB undergoes a significant change from 30 to 298 K where changes in other N-H...O interactions are almost negligible. There is a good agreement between the calculated (14)N NQR parameters and reported experimental data.

A systematic study on hydrogen bond interactions in sulfabenzamide: DFT calculations of the N-14, O-17, and H-2 NQR parameters.

A systematic computational study was carried out to characterize the hydrogen bond, HB, interactions of sulfabenzamide crystal structure by DFT calculations of electric field gradient, EFG, tensors at the sites of 14N, 17O, and 2H nuclei. The computations were performed with the B3LYP and B3PW91 DFT methods and 6-311+G and 6-311++G* standard basis sets using the Gaussian 98 package. To perform the calculations, a hydrogen-bonded heptameric cluster of sulfabenzamide was created by X-ray coordinates where the hydrogen atom positions were optimized and the EFG tensors were calculated for the target molecule. Additional optimization and EFG calculations were also performed for crystalline monomer and an isolated gas-phase sulfabenzamide. The calculated EFG tensors were converted to the experimentally measurable nuclear quadrupole resonance, NQR, parameters: quadrupole coupling constant, C(Q), and asymmetry parameter, eta(Q). The results reveal that the geometrical and NQR parameters of the optimized isolated gas-phase and crystalline phase are different. In addition, the difference between the calculated NQR parameters of the monomer and the target molecule shows how much H-bonding interactions affect the EFG tensors of each nucleus. The evaluated NQR parameters reveal that due to the contribution of the target molecule to N-H...O and C-H...O hydrogen bond interactions, the EFG tensors at the sites of N1, O3 and H1 undergo significant changes from monomer to the target molecule in cluster. These features reveal the major role of N-H...O type intermolecular HBs in cluster model of sulfabenzamide which the presence of these interactions can lead to polymorphism directly related to the drug activity and related properties.