Composite membrane containing phosphoric acid (PA) for possible use in a fuel cell was prepared by radiation-induced grafting of 1-vinylimidazole (1-VIm) onto poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by protonation with PA doping. The preparation procedure involved three steps: (i) irradiation of ETFE films by an electron beam, (ii) grafting of 1-VIm onto the irradiated films under selected conditions and (iii) doping the grafted film with PA. The membrane composition, thermal properties and thermal stability were evaluated using Fourier-transformed infrared spectroscopy, thermogravimetric analysis and differential scanning calorimetry, respectively. The obtained membrane was found to have a degree of grafting of 54% and 6.6 mmol PA per poly-VIm repeating unit with ionic conductivity of 140 mS cm À1 at 120 C and *20% relative humidity. The overall results suggest that the membrane has a promising combination of physicochemical properties appealing for possible application in polymer electrolyte membrane fuel cell above 100 C.
We present a synthesis of large-area single-layer graphene on copper substrate using a refined cooking palm oil, a natural single carbon source, by a home-made spray injector-assisted chemical vapor deposition system. The effects of the distance between spray nozzle and substrate, and growth temperature are studied. From Raman mapping analysis, shorter distance of 1 cm and temperature of around 950 °C lead to the growth of large-area single-layer graphene with a coverage up to 97% of the measured area size of 6400 μm 2 . The crystallinity of the grown single layer graphene is relatively good due to high distribution percentage of FWHM values of 2D band that is below 30 cm −1 . However, the defect concentration is relatively high, and it suggests that a flash-cooling technique needs to be introduced.
The dissociation of zinc ions (Zn2+) from vapor-phase zinc acetylacetonate, Zn(C5H7O2)2, or Zn(acac)2 and its adsorption onto graphene oxide via atomic layer deposition (ALD) were studied using a quantum mechanics approach. Density functional theory (DFT) was used to obtain an approximate solution to the Schrödinger equation. The graphene oxide cluster model was used to represent the surface of the graphene film after pre-oxidation. In this study, the geometries of reactants, transition states, and products were optimized using the B3LYB/6-31G** level of theory or higher. Furthermore, the relative energies of the various intermediates and products in the gas-phase radical mechanism were calculated at the B3LYP/6-311++G** and MP2/6-311 + G(2df,2p) levels of theory. Additionally, a molecular orbital (MO) analysis was performed for the products of the decomposition of the Zn(acac)2 complex to investigate the dissociation of Zn2+ and the subsequent adsorption of H atoms on the C5H7O2 cluster to form acetylacetonate enol. The reaction energies were calculated, and the reaction mechanism was accordingly proposed. A simulation of infrared (IR) properties was performed using the same approach to support the proposed mechanism via a complete explanation of bond forming and breaking during each reaction step.
We report the growth of gallium-based compounds, i.e., gallium oxynitride (GaON) and gallium oxide (Ga2O3) on multilayer graphene (MLG) on insulator using a mixture of ammonium nitrate (NH4NO3) and gallium nitrate (Ga(NO3)3) by electrochemical deposition (ECD) method at room temperature (RT) for the first time. The controlling parameters of current density and electrolyte molarity were found to greatly influence the properties of the grown structures. The thicknesses of the deposited structures increase with the current density since it increases the chemical reaction rates. The layers grown at low molarities of both solutions basically show grain-like layer with cracking structures and dominated by both Ga2O3 and GaON. Such cracking structures seem to diminish with the increases of molarities of one of the solutions. It is speculated that the increase of current density and ions in the solutions helps to promote the growth at the area with uneven thicknesses of graphene. When the molarity of Ga(NO3)3 is increased while keeping the molarity of NH4NO3 at the lowest value of 2.5 M, the grown structures are basically dominated by the Ga2O3 structure. On the other hand, when the molarity of NH4NO3 is increased while keeping the molarity of Ga(NO3)3 at the lowest value of 0.8 M, the GaON structure seems to dominate where their cubic and hexagonal arrangements are coexisting. It was found that when the molarities of Ga(NO3)3 are at the high level of 7.5 M, the grown structures tend to be dominated by Ga2O3 even though the molarity of NH4NO3 is made equal or higher than the molarity of Ga(NO3)3. When the grown structure is dominated by the Ga2O3 structure, the deposition process became slow or unstable, resulting to the formation of thin layer. When the molarity of Ga(NO3)3 is increased to 15 M, the nanocluster-like structures were formed instead of continuous thin film structure. This study seems to successfully provide the conditions in growing either GaON-dominated or Ga2O3-dominated structure by a simple and low-cost ECD. The next possible routes to convert the grown GaON-dominated structure to either single-crystalline GaN or Ga2O3 as well as Ga2O3-dominated structure to single-crystalline Ga2O3 structure have been discussed.
We demonstrate a systematic computational analysis of the measured optical and charge transport properties of the spray pyrolysis-grown ZnO nanostructures, i.e. nanosphere clusters (NSCs), nanorods (NRs) and nanowires (NWs) for the first time. The calculated absorbance spectra based on the time-dependent density functional theory (TD-DFT) shows very close similarity with the measured behaviours under UV light. The atomic models and energy level diagrams for the grown nanostructures were developed and discussed to explain the structural defects and band gap. The induced stresses in the lattices of ZnO NSCs that formed during the pyrolysis process seem to cause the narrowing of the gap between the energy levels. ZnO NWs and NRs show homogeneous distribution of the LUMO and HOMO orbitals all over the entire heterostructure. Such distribution contributes to the reduction of the band gap down to 2.8 eV, which has been confirmed to be in a good agreement with the experimental results. ZnO NWs and NRs exhibited better emission behaviours under the UV excitation as compared to ZnO NSCs and thin film as their visible range emissions are strongly quenched. Based on the electrochemical impedance measurement, the electrical models and electrostatic potential maps were developed to calculate the electron lifetime and to explain the mobility or diffusion behaviours in the grown nanostructure, respectively.
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