电化学沉积技术制备LiNiO2薄膜及表征

Well-crystallized LiNiO₂ thin films were prepared directly on nickel substrates in LiOH solution by constant current electrochemical deposition technique at 95 ℃. The as-prepared LiNiO₂ thin films were characterized by using XRD, SEM and XPS, and the results reveal that the as-prepared LiNiO₂ thin films are dense and uniform in surface and show hexagonal structure. The influence of processing parameters such as reaction temperature, duration, electrical current density as well as the concentration of LiOH solution on the structure and morphologies of as-prepared LiNiO₂ thin films were studied，and the preferable electrochemical processing conditions for preparing LiNiO₂ thin films were suggested.     

化学浴沉积法制备高取向钒酸铋薄膜

Highly oriented BiVO₄ films were synthesized on glass substrates by modified chemical bath deposition (CBD). The influence of the deposition parameters as temperature and time of deposition on the rate of process and the quality of BiVO₄ films was studied by XRD, Raman Spectroscopy and SEM. The film deposited at 90 ℃ for 12 h was dense and uniform. The BiVO₄ thin film under this optimal depositing conditions was consisted of octagonal crystalline grains in a narrow size distribution with an average size of about 7 μm, showing a (004) preferential orientation.     

离子层气相反应法(ILGAR)制备CuInS2薄膜的研究

CuInS₂ thin films have been prepared by ion layer gas reaction (ILGAR) using C₂H₅OH as solvent, CuCl and InCl₃ as reagents and H₂S gas as sulfuration source. The effects of cationic concentrations and numbers of cycle on the properties of CuInS₂ film were investigated. The chemical composition, crystalline structure, surface topography, deposited rate, optical and electronic properties of the films were characterized by X-ray diffractrometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), ultraviolet-visible spectrometry (UV-Vis) and Hall System. The results show that the crystalline of CuInS₂ thin films and the deposition rate have been improved with the increase of cationic concentration, while CuxS segregation phases appear with further increasing cationic concentration. The deposition rate is close to constant as cationic concentration is fixed. CuInS₂ thin film derived form lower cationic concentration is uniform, compact and good in adhesion to the substrates. The absorption coefficient of CuInS₂ thin films is larger than 10⁴ cm^-1, and the band gap E_g is in the range of 1.30～1.40 eV. The dark resisitivity of the thin film decreases from 50 to 10 Ω·cm and the carrier concentration ranges are over 10¹⁶ cm^-3.     

电沉积HA/TiO2复合涂层的结合强度和热稳定性研究

HA/TiO₂ composite coating were fabricated via adding TiO₂ powder in the electrolyte by electrodeposition. The influence of current density and deposition time on the content of TiO₂ in the coating, the influence of the content of TiO₂ in the coating on the bonding strength of coating and the influence of sintering temperature on the structure and the bonding strength of coating were investigated. The experiment results show that the content of TiO₂ in the coating increase with reducing the current density and prolonging the deposition time, the bonding strength improve with increasing the content of TiO₂ in the coating, which can obtain 18.7 MPa when the weight percent TiO₂ in the coating attain 72.2 %. The addition of TiO₂ in the coating reduces the thermal expansion coefficient of the coating, improves the bonding strength of coating and changes the fracture mechanism of the coating from adhesion failure to cohesive failure. HA in the composite coatings is decomposed by the catalysis reaction of TiO₂ at the temperature of sinter 850 ℃. Differential scanning calorimetry and X-ray diffractometry analyses showed that the chemical reaction between HA and TiO₂ lead to the product are α-TCP and CaTiO₃ at the temperature of sinter 1200 ℃. In order to prevent the coating from decomposing and attain hign bonding strength, the sintering temperature should be less than 820 ℃.     

Ni/AC电催化剂在中性溶液中的析氢电催化性能

The Ni/active carbon (AC) electro-catalyst was prepared by chemical reduction method using coconut carbon as the support. Morphologies and structures of Ni/AC were measured and characterized by X-ray diffraction and scanning electron microscopy. The activity of the Ni/AC membrane electrodes were studied in the neutral electrolyte using Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The results showed that the average size of nickel particles on the active carbon were in nano-size range. The exchange current density of hydrogen evolution reaction (HER) of Ni/AC electro-catalysts was seventy-five times more than pure nickel, so Ni/AC electro-catalysts had better electro-catalytic activity. In 1 mol·L^-1 NaCl electrolyte, the Tafelian behavior′s hydrogen evolution reaction (HER) of Ni/AC electro-catalyst at high over-potential existed in two Tefal regions. These two regions were named as “regionⅠ:0.318～0.456 V” and “regionⅡ: 0.120～0.288 V”. The rate step of regionⅠ was electron transference step. The rate step of region Ⅱ was concentration polarization.     

铈掺杂纳米ZnO结构与室温脱硫性能的相关性研究

Nano-ZnO desulfurizer doped with cerium was prepared by homogeneous precipitation. The bulk and surface structures were characterized by TG-DTA, XRD, XPS and TEM. The desulfurizing performance at ambient temperature was studied. The results show that at ambient temperature the desulfurizing activities of nano-Ce-ZnO desulfurizer are closely related to the particle size, the electron density on desulfurizer surface and the quantity of active sites. Compared with nano-ZnO, nano-Ce-ZnO desulfurizer calcined at 270 ℃ showed smaller particle size and higher surface electron density, which favored the adsorption and reaction of H₂S, resulting in improved desulfurizing activity at ambient temperature since the quantity of Zn^(2-δ)+ became greater by electron gain of zinc ion from cerium ion. The tendency for zinc and cerium to be separated out as individual oxide from Ce-ZnO desulfurizer would increase as the calcination temperature was raised. The enrichment of cerium on the surface of ZnO made decrease the active sites for H₂S adsorption, which led to the decrease in desulfurization activity at ambient temperature.     

纳米氧化镍的制备及其电容特性研究

Nano-nickel oxide was synthesized by chemical deposition of nano-nickel hydroxide followed by heat-treatment in air at 300 ℃. The structure of the sample was studied by XRD, TEM, etc. The electrochemical characteristics of the sample were studied by Cyclic Voltammetry and constant current charge/discharge. The results showed that the structure of nickel oxide was cubic and the shape was acicular. The specific capacitance of the nickel oxide was about 130 F·g^-1 in the 9.0 mol·L^-1 KOH solution. The effects of scan speed, heating temperature and cycling on the specific capacitance were discussed.     

纳米氧化锰电极材料的制备和电容特性研究

The nano-MnO₂ as active electrode material for supercapacitor was synthesized by solid-state reaction between KMnO₄ and manganese acetate at room temperature. The products annealed at 100 ℃ and 200 ℃ were characterized by XRD and TEM. The results showed the sample annealed at 100 ℃ was poorly crystallized phase with an average grain size of <20 nm. Electrochemical performances of manganese oxide electrode were investigated by cyclic voltammetry and constant current charge/discharge. The manganese oxide electrode annealed at 100 ℃ in 1 mol·L^-1 Na₂SO₄ aqueous electrolyte exhibited excellent capacitive behavior between -0.2 and +0.8 V (vs SCE). By 5 mA and 10 mA constant current charge/discharge, the nano-MnO₂ annealed at 100 ℃ can provide a specific capacitance of 158.5 F·g^-1 and 151.2 F·g^-1, respectively.     

Preparation and characterization of a new polymer electrolyte (PEO:NaClO3) for battery application

A new sodium-ion conducting thin-film polymer electrolyte based on the poly(ethylene oxide) (PEO) system has been prepared by a solution-casting method. Characterization by XRD, IR, and AC conductivity and Wagner's polarization were carried out on these thin-film electrolytes. From the transference number experiment it was found that the charge transport in these electrolytes is mainly due to ions. Conductivity studies show that the conductivity value of the PEO:NaClO₃ complex increases with the increase of salt concentration. An increase in the conductivity and a change in the cell parameters for the electrolyte system were found by the addition of the low molecular weight dimethylformamide or propylene carbonate as plasticizers. The cell parameters of these electrolyte systems were measured from a discharge study of the cell with the application of a load of 100 kΩ at room temperature in the common cell configuration Na|electrolyte|MnO₂. The open circuit voltage ranges from 2.02 V to 2.46 V and the short circuit current ranges from 570 μA to 1030 μA. Electronic Publication     

纳米BaFe12O19永磁铁氧体的制备、结构和磁性的研究

In this paper, the nanometer permanent magnetic BaFe₁₂O₁₉ powder was synthesized by a novel method of independent nucleation and crystallization steps and subsequent heat treatment,during the synthesis, Ba(NO₃)₂, Fe(NO₃)₂ and NH₄HCO₃·NH₂COONH₄ were used as starting materials. The effect of crystallization process and heat treatment conditions on the particle size, microstructure and magnetic properties of powder was studied by using XRD, TEM and vibration sample magnetometometer techniques.XRD results showed that the hematite, α-Fe₂O₃, was the main phase in the powder at heat treatment temperatures below 650℃ and its amount in the powder was decreased with increasing temperature and small amount of α-Fe₂O₃ was still remained after being heated at 900℃ for 8hrs. BaFe₁₂O₁₉ was formed about 650℃ and its amount increased in the powder as temperature raised and the higher temperature was needed to attain considerable amount of BaFe₁₂O₁₉ and ideal nanometer BaFe₁₂O₁₉ particle in the powder. The temperature between 40℃～60℃ in the crystallization process was favor to the formation of good BaFe₁₂O₁₉ crystal and to the good magnetic properties of the powder. TEM showed that the particle size in the powder increased with the enhancement of the temperature and the powder crystallized at 40℃ and heated at 800℃ for 8hrs afterwards had a very homogenous particle size distribution, and that the powder heated at 900℃ for 8hrs with the same crystalline condition as the former had a typical hexagonal shape and a chain aggregation. Specific saturation and residential magnetizations and coercive force of the powder increased mono-tonically with the increase of temperature, and reached 39.86A·m²·kg^-1, 23.96A·m²·kg^-1, 480kA·mg^-1 at 900℃, respectively.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.