Theoretical investigation on action mechanism and mollifying efficacy of propellant stabilizers.

CONTEXT: This project performed quantum chemical computation, through kinetic and thermodynamic analyses to compare relative reactivity, reaction rate, and equilibrium composition from the possible pathways in connection with stabilizer-nitrodioxide reactions to determine the stability of the materials for practical application. Corresponding achievements have promoted the use of N-methyl-p-nitroaniline (MNA) and dinitrophenyl malonamide series (M3, M4, and M5) stabilizers as high priorities for selection. METHODS: The Gaussian 09 program (G09) (Frisch et al 2009) and density functional theory (DFT) calculations with the B3LYP/6-31G(d,p) function were performed to obtain related geometric and thermodynamic energy data for the molecular systems in this study. The synchronous transit-guided quasi-Newton method (STQN) (Peng and Schlegel Isr J Chem 33:49, 1993) was applied through the QST3 procedure to identify single imaginary frequency-valued transition-state species. The related reaction rate constant (k) and pre-exponential factor (A) were obtained, based on transition state theory (Su 2008), using Eqs. 11 and 12.

A novel method for preparation of Zn-doped CuInS2 solar cells and their photovoltaic performance.

In this study, a novel method was proposed to synthesize high quality Zn-doped CuInS2 nanocrystals under high frequency magnetic field at ambient conditions. The magnetic Zn-doping gave superparamagnetic heating of the resulting nanocrystals via magnetic induction, causing an accelerating growth rate of the doped CuInS2 under ambient conditions faster than conventional autoclave synthesis. Shape evolution of the Zn-doped CuInS2 nanocrystals from initially spherical to pyramidal, to cubic, and finally to a bar geometry was detected as a function of time of exposure to magnetic induction. These colloidal solvents with different shaped nanocrystals were further used as "nanoink" to fabricate a simple thin film solar device; the best efficiency we obtained of these crystals was 1.01% with a 1.012 µm thickness absorber layer (bar geometry). The efficiency could be promoted to 1.44% after the absorber was thickened to 2.132 µm.

A preliminary study on the synthesis and characterization of multilayered Ag/Co magnetic nanowires fabricated via the electrodeposition method.

A single-bath electrodeposition method was developed to integrate multilayer Ag/Co nanowires with a commercial anodic alumina oxide (AAO) template with a pore diameter of 100-200 nm. An electrolyte system containing silver nitride and cobalt sulfide was studied using cyclic voltammetry, and the electrodeposition rate was varied to optimize the electrodeposition conditions. A constant stepwise potential and a variable cation ratio of [Co²âº]/[Ag⁺] were used during electrodeposition. After the dissolution of the template in aqueous NaOH solution, multilayered Ag/Co nanowires were obtained with a composition of [Co]/[Ag80Co20], as identified by XRD and TEM, when [Co²âº]/[Ag⁺] = 150. By annealing at 200°C for 1 h, uniformly structured (Co99.57/Ag100) nanowires were obtained. Compared with pure Co nanowires, the magnetic hysteresis loops showed a greater magnetic anisotropy for (Co99.57/Ag100) nanowires than for pure Co nanowires, corresponding to a change in the easy axis upon magnetization.

Using Graphene-Based Composite Materials to Boost Anti-Corrosion and Infrared-Stealth Performance of Epoxy Coatings.

Corrosion prevention and infrared (IR) stealth are conflicting goals. While graphene nanosheets (GN) provide an excellent physical barrier against corrosive agent diffusion, thus lowering the permeability of anti-corrosion coatings, they have the side-effect of decreasing IR stealth. In this work, the anti-corrosion properties of 100-µm-thick composite epoxy coatings with various concentrations (0.01-1 wt.%) of GN fillers thermally reduced at different temperatures (300 °C, 700 °C, 1100 °C) are first compared. The performance was characterized by potentiodynamic polarization scanning, electrochemical impedance spectroscopy, water contact angle and salt spray tests. The corrosion resistance for coatings was found to be optimum at a very low filler concentration (0.05 wt.%). The corrosion current density was 4.57 × 10-11 A/cm2 for GN reduced at 1100 °C, showing no degradation after 500 h of salt-spray testing: a significant improvement over the anti-corrosion behavior of epoxy coatings. Further, to suppress the high IR thermal signature of GN and epoxy, Al was added to the optimized composite at different concentrations. The increased IR emissivity due to GN was not only eliminated but was in fact reduced relative to the pure epoxy. These optimized coatings of Al-GN-epoxy not only exhibited greatly reduced IR emissivity but also showed no sign of corrosion after 500 h of salt spray test.

Improved current density with Al2O3 coated ZnO nanorod in hybrid solar cell.

Heterojunction photovoltaic devices consisting of hybrid p-type organic Cu-phthalocyanine and inorganic n-type Al2O3 nanoparticle-coated aligned ZnO nanorods were fabricated. With microwave treatment, an interaction occurred between the Al2O3 and ZnO, as evidenced from TEM image. This interaction shifts the absorption peak of the aligned nanorods from the UV region to visible light and subsequently causes more charge generation. For 5 mol% Al2O3 nanoparticle-coated aligned ZnO nanorods treated with microwaves of 600 W for 300 sec, the maximum incident photon to electron conversion and energy conversion efficiencies under simulated sunlight of AM1.5G (10 mW/cm2) are 0.036 mA and 1.32%, respectively.

Fabrication and characterization of Mg-doped ZnO nanorod arrays.

Photoelectronic characteristics are investigated in well-aligned MgO-coated ZnO nanorods (MgO/ZnO nanocables) grown on Si substrates buffered with ZnO film at a low temperature by solution techniques. Transmission electron microscopy shows that a rough surface was observed for the MgO-coated ZnO nanorods due to deposition of MgO nanoparticles on the surface of the ZnO nanorods. However, after annealed at high temperatures, the surface of the MgO-coated ZnO nanorods was flattened to form Mg-doped ZnO nanorods. Photoluminescence spectra of Mg-doped ZnO nanorods displayed a blue shift of the near-band-edge emission with increasing annealing temperature indicative of an increase in the band gap of the MgZnO alloy due to diffusion of the Mg atoms into the ZnO nanorods. In contrast, no blue shift was detected for the samples annealed in H2/N2 (5%/95%) reduction atmosphere but a blue emission was detected at 800 degrees C, indicating that MgO diffusion process may produce a new luminescent center to emit the blue emission in H2/N2 reduction atmosphere.

Synthesis and Characterization of Hybrid Metal Zeolitic Imidazolate Framework Membrane for Efficient H2/CO2 Gas Separation.

In this paper, we propose mixed metal ions in the node of the zeolitic imidazolate framework (ZIF) structure. The hybrid metal ZIF is formed for the gas separation of hydrogen and carbon dioxide. In the first stage, the nanoparticles were prepared as a coating on a substrate, and acting as secondary growing nuclei. The hybrid metal ZIF structures were characterized by X-ray diffractometry (XRD) and Fourier transform infrared spectroscopy (FTIR). N2 adsorption-desorption isotherms determined surface area, and scanning electron microscopy (SEM) was used to observe the microstructure and surface morphology. The hybrid metal ZIF-8-67 powder had the largest surface area (1260.40 m2 g-1), and the nanoparticles (100 nm) could be fully dense-coated on the substrate to benefit the subsequent membrane growth. In the second stage, we prepared the hybrid metal ZIF-8-67 membrane on the pre-seeding substrate with mixed metal nanoparticles of cobalt and zinc, by the microwave hydrothermal method. Cobalt ions were identified in the tetrahedral coordination through UV-Vis, and the membrane structure and morphology were determined by XRD and SEM. Finally, a gas permeation analyzer (GPA) was used to determine the gas separation performance of the hybrid metal ZIF-8-67 membrane. We successfully introduced zinc ions and cobalt ions into the ZIF structure, where cobalt had a strong interaction with CO2. Therefore, GPA analysis showed an excellent H2/CO2 separation factor due to lower CO2 permeability. The CO2 permeance was ~0.65 × 10-8 mol m-2 s-1 Pa-1, and the separation factors for H2/CO2 and H2/N2 were 9.2 and 2.9, respectively. Our results demonstrate that the hybrid metal ZIF-8-67 membrane has a superior H2/CO2 separation factor, which can be attributed to its very high specific surface area and structure. Based on the above, hybrid metal ZIF-8-67 membranes are expected to be applied in hydrogen or carbon dioxide gas separation and purification.

Synthesis and Formation Mechanism of Limestone-Derived Porous Rod Hierarchical Ca-based Metal-Organic Framework for Efficient CO2 Capture.

Limestone is a relatively abundant and low-cost material used for producing calcium oxide as a CO2 adsorbent. However, the CO2 capture capacity of limestone decreases rapidly after multiple carbonation/calcination cycles. To improve the CO2 capture performance, we developed a process using limestone to transform the material into a rod Ca-based metal-organic framework (Ca-MOF) via a hydrothermal process with the assistance of acetic acid and terephthalic acid (H2BDC). The structural formation of rod Ca-MOF may result from the (200) face-oriented attachment growth of Ca-MOF sheets. Upon heat treatment, a highly stable porous rod network with a calcined Ca-MOF-O structure was generated with a pore distribution of 50-100 nm, which allowed the rapid diffusion of CO2 into the interior of the sorbent and enhanced the CO2 capture capacity with high multiple carbonation-calcination cycle stability compared to limestone alone at the intermediate temperature of 450 °C. The CO2 capture capacity of the calcined porous Ca-MOF-O network reached 52 wt% with a CO2 capture stability of 80% after 10 cycles. The above results demonstrated that rod Ca-MOF can be synthesized from a limestone precursor to form a porous network structure as a CO2 capture sorbent to improve CO2 capture performance at an intermediate temperature, thus suggesting its potential in environmental applications.

Multi-Metals CaMgAl Metal-Organic Framework as CaO-based Sorbent to Achieve Highly CO2 Capture Capacity and Cyclic Performance.

In this study, Ca-based multi-metals metal-organic framework (CaMgAl-MOF) has been designed as precursor material for carbon dioxide (CO2) capture to enhance the CO2 capture capacity and stability during multiple carbonation-calcination cycles. The CaMgAl-MOFs were constructed from self-assembly of metal ions and organic ligands through hydrothermal process to make metal ions uniformly distributed through the whole structure. Upon heat treatment at 600 °C, the Ca-based multi-metals CaMgAl-MOF would gradually transform to CaO and MgO nanoparticles along with the amorphous aluminum oxide distributed in the CaO matrix. XRD, Fourier transform infrared (FTIR), and SEM were used to identify the structure and characterize the morphology. The CO2 capture capacity and multiple carbonation-calcination cyclic tests of calcined Ca-based metal-organic framework (MOF) (attached with O and indicated as Ca-MOF-O) were performed by thermal gravimetric analysis (TGA). The single metal component calcined Ca-MOF sorbent have the highest CO2 capture capacity up to 72 wt.%, but a lower stability of 61% due to severe particle aggregation. In contrast, a higher Ca-rich MOF oxide sorbent with tailoring the Mg/Al ratios, Ca0.97Mg0.025Al0.005-MOF-O, showed the best performance, not only having the high stability of ~97%, but also maintaining the highest capacity of 71 wt.%. The concept of using Ca-based MOF materials combined with mixed-metal ions for CO2 capture showed a potential route for achieving efficient multiple carbonation-calcination CO2 cycles.

Waffle-Like Carbons Combined with Enriched Mesopores and Highly Heteroatom-Doped Derived from Sandwiched MOF/LDH/MOF for High-Rate Supercapacitor.

Supercapacitors (SCs) are promising for powering mobile devices, electric vehicles and smart power grids due to their fast charge/discharge rate, high power capability and robust cycle stability. Nitrogen-doped porous carbons are great alternatives because they provide pseudocapacitance without losing their power rate. Nanoporous carbon derived from metal organic frameworks (MOFs) is an ideal precursor for preparing heteroatom-doped carbons due to their abundant nitrogen contents and incredible specific surface areas. However, severe aggregations and the leakage of nitrogen can occur during harsh carbonization. In this study, we used CoAl-LDH (cobalt aluminum layered double hydroxide) as an in-situ growth substrate, allowing Co-based MOF to uniformly grow onto the CoAl-LDH to form a sandwiched MOF/LDH/MOF structure. After acid etching, we obtained waffle-like nanoporous carbons (WNPC). WNPC exhibited high nitrogen and oxygen retention (7.5 wt% and 9.1 wt%) and a broad mesopores distribution with specific surface areas of 594 m2g-1, which promoted a sieving effect. This renders a specific capacitance of 300.7 F·g-1 at 1 A·g-1 and the high retention (72%) of capacitance at 20 A·g-1, ensuring its use at high-rate supercapacitor electrodes. Finally, the WNPC symmetric supercapacitor reaches a superior specific energy of 27 W·h·kg-1 at a power of 500 W·kg-1, and a good cycle stability (85% capacitance retention after 10,000 cycles).

Neuroprotective effects of resveratrol on MPTP-induced neuron loss mediated by free radical scavenging.

Resveratrol is a natural polyphenol and possesses many biological functions such as anti-inflammatory activity and protection against atherosclerosis and myocardial infraction. Parkinson's disease is a common progressive neurodegenerative disease. 1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) is the most useful neurotoxin to induce Parkinsonism. The present study was carried out to elucidate the neuroprotective effect and possible mechanism of resveratrol on MPTP-induced striatal neuron loss. Sixty adult Balb/c mice were divided into four groups: sham operation, MPTP treatment (30 mg/kg, i.p.), MPTP combined with resveratrol administration (20 mg/kg, i.v.), and resveratrol treatment alone. Microdialysis and high-performance liquid chromatography were used to analyze dihydroxybenzoic acid (DHBA) that reflected the hydroxyl radical level. In the present study, we found MPTP chronic administration significantly induced motor coordination impairment in mice. After MPTP administration, the hydroxyl radical levels in substantia nigra were also significantly elevated and animals displayed severe neuronal loss. Resveratrol administration significantly protected mice from MPTP-induced motor coordination impairment, hydroxyl radical overloading, and neuronal loss. Our results demonstrated that resveratrol could elicit neuroprotective effects on MPTP-induced Parkinsonism through free radical scavenging.