A hybrid nonaqueous electrochemical supercapacitor using nano-sized iron oxyhydroxide and activated carbon

A beta-iron oxyhydroxide (FeOOH) was synthesized via a hydrolyzing route and investigated as a lithium intercalation host. It delivers a capacity of about 170 mAh/g and exhibits good cycling performance when charged/discharged in the voltage range from 1.6 V to 3.3 V. For the first time we have confirmed that FeOOH is suitable for using it as a negative electrode for hybrid electrochemical supercapacitor assembled with an activated carbon positive electrode in 1.0 M LiPF₆ ethylene carbonate/dimethyl carbonate (EC/DMC, 1:2 in volume) solution. The cell reveals a slightly sloping voltage profile from 0 V to 2.8 V and gives an estimated specific energy of 45 Wh/kg based on the total weight of two electrode materials, approximately two times of carbon/carbon electrochemical double layer capacitors. The hybrid supercapacitor shows a good cycling performance, it remains approximately 96% of initial capacity after 800 cycles at a charge/discharge rate of 4 C. The capacitor also shows a desirable rate capability, even at 10 C discharge rate, it holds 80% of capacity compared with that at 1 C discharge rate.     

The effect of substituents on the extraction behavior of hydroxamic acids

The extraction behavior of several alkyl-substituted hydroxamic acids in chloroform solution with several metal ions is described. Among the N-phenylacylhydroxamic acids used, those with o-alkyl substituents on either the phenyl or acyl ring generally do not extract metals, apparently because of steric problems at the O=CNO^? chelation site. An improved synthesis of substituted hydroxamic acids is reported.     

Catalytic, highly enantio- and diastereoselective pinacol coupling reaction with a new tethered bis(8-quinolinolato) ligand

A new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH), is developed. Its chromium complex, TBOxCrCl (3 mol %), effectively catalyzes the pinacol coupling reaction of aromatic aldehydes at room temperature with high yield (up to 94%), high diastereoselectivity (up to dl:meso = 98:2), and high enantioselectivity (up to 98%). The scope of the present method turns out not to be limited to aromatic aldehyde derivatives, as cyclohexanecarboxaldehyde undergoes pinacolization as well (44% yield, dl:meso = 93:7, 84% ee). The method provides an efficient access to enantioenriched 1,2-diols.     

Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

Low-energy paths for the unimolecular decomposition of CH3OH: a G2M/statistical theory study

The potential energy surface (PES) of the CH3OH system has been characterized by ab initio molecular orbital theory calculations at the G2M level of theory. The mechanisms for the decomposition of CH3OH and the related bimolecular reactions, CH3 + OH and 1CH2 + H2O, have been elucidated. The rate constants for these processes have been calculated using variational RRKM theory and compared with available experimental data. The total decomposition rate constants of CH3OH at the high- and low-pressure limits can be represented by k infinity = 1.56 x 10(16) exp(-44,310/T) s-1 and kAr0 = 1.60 x 10(36) T-12.2 exp(-48,140/T) cm3 molecule-1 s-1, respectively, covering the temperature range 1000-3000 K, in reasonable agreement with the experimental values. Our results indicate that the product branching ratios are strongly pressure dependent, with the production of CH3 + OH and 1CH2 + H2O dominant under high (P > 10(3) Torr) and low (P < 1 atm) pressures, respectively. For the bimolecular reaction of CH3 and OH, the total rate constant and the yields of 1CH2 + H2O and H2 + HCOH at lower pressures (P < 5 Torr) could be reasonably accounted for by the theory. For the reaction of 1CH2 with H2O, both the yield of CH3 + OH and the total rate constant could also be satisfactorily predicted theoretically. The production of 3CH2 + H2O by the singlet to triplet surface crossing, predicted to occur at 4.3 kcal mol-1 above the H2C...OH2 van der Waals complex (which lies 82.7 kcal mol-1 above CH3OH), was neglected in our calculations.     

Synthesis and Photophysical and Electrochemical Study of Tyrosine Covalently Linked to High‐Valent Copper(III) and Manganese(IV) Complexes

As bio‐inspired chemical model of the oxygen‐evolving complex (OEC) in photosystem II, a new tyrosine‐modified corrole ligand 3 and its high‐valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of 1a and 2a . The corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at ?0.17 and 0.77 V vs. Ag/Ag⁺, respectively.     

Synthesis and characterization of monodispersed core-shell spherical colloids with movable cores

Gold nanoparticles have been conformally coated with amorphous silica (using a sol-gel method) and then an organic polymer (via surface-grafted, atom transfer radical polymerization) to form spherical colloids with a core-double-shell structure. The thickness of silica and polymer shells could be conveniently controlled in the range of tens to several hundred nanometers by changing the concentration of the reagent and/or the reaction time. Selective removal of the silica layer (through etching in aqueous HF) led to the formation of hollow polymer beads containing movable gold cores. This new form of core-shell particles provides a unique system for measuring the feature size and transport property associated with hollow particles. In one demonstration, we showed that the thickness of a closed polymer shell could be obtained by mapping the electrons backscattered from the core and shell. In another demonstration, the plasmon resonance band of the gold cores was used as an optical probe to follow the diffusion kinetics of chemical reagents across the polymer shells.     

A novel method of the separation/preconcentration and determination of trace molybdenum(VI) in water samples using microcrystalline triphenylmethane loaded with salicyl fluorone

It is the first time that triphenylmethane was used as an adsorbent to preconcentrate and separate trace amount of molybdenum in water samples. The effects of different parameters, such as acidity, stirring time and various metal ions, the amounts of triphenylmethane and salicyl fluorine, etc. on the enrichment yield of molybdenum have been studied to optimize the experimental conditions. Under the optimum conditions, molybdenum can be adsorbed on the surface of microcrystalline triphenylmethane loaded with salicyl fluorone by the intermolecular action strength. The possible reaction mechanism for the enrichment of molybdenum was discussed in detail in this paper. Mo(VI) can be completely separated from Pb(II), Co(II), Cu(II), Cr(III), Ni(II), Hg(II), Zn(II), Cd(II), Fe(III) and Al(III) in the solution. The proposed method was successfully applied to the determination of trace amount of molybdenum in various water samples by spectrophotometry after preconcentration using microcrystalline triphenylmethane. The preconcentration factor is from 83 (500 ml water sample was enriched to 6.0 ml) to 166 (1000 ml water sample was enriched to 6.0 ml). The detection limit is 1.3 × 10⁻⁵ mg l⁻¹ and the linearity is maintained in the concentration range 3.8 × 10⁻³ to 0.36 mg l⁻¹ with a correlation coefficient of 0.9998. The recoveries are in the range of 93.5-104%. The relative standard deviation is 1.8-2.9%. Analytical results obtained with this novel method are very satisfactory.     

Repeatability and pattern recognition of bacterial fatty acid profiles generated by direct mass spectrometric analysis of in situ thermal hydrolysis/methylation of whole cells

Direct CI mass spectrometry profiling of fatty acid methyl esters (FAMEs) from in situ thermal hydrolysis/methylation (THM) of whole bacterial cells with tetramethylammonium hydroxide (TMAH) has been demonstrated as a potential method for real time and fieldable detection/identification of microorganisms. Bacillus anthracis (Ames), Yersinia pestis (Nair. Kenya), Vibrio cholerae (E1 Tor), Brucella melitensis (Abortus wild) and Francisella tularensis (LVS vaccine) were profiled by this method during a 10-month period. Repeatability of the in situ FAME data was calculated using one-way analysis of variance (ANOVA) and a t-test. Artificial neural network (ANN) and multivariate statistics of the FAME profiles were also compared for bacterial identification/classification. Equivalent results were obtained with a multivariate rule building expert system (MuRES) and the ANN. However, the ANN analysis required much less computer time and was deemed the best choice for this application. In situ THM FAME profiles of the bacterial samples provided comparable results with those obtained from the Microbial Identification System (MIDI) (Newark, DE) wet chemistry-gas chromatographic based system.     

电化学检测在流动注射分析中的应用

评述了近几年来电化学检测在流动注射分析中的应用，展望了流动注射电化学分析法的发展动向。