碳酸铝铵热分解制备纳米氧化铝粉体

Nanosized alumina powders were prepared from Al(NO₃)₃·9H₂O and (NH₄)₂CO₃ through the synthesis of ammonium aluminium carbonate hydroxide (AACH) and followed by calcination. TG-DTA， XRD， TEM and BET were employed to study the process of AACH thermal decomposition and to characterize the products obtained. The results show that high purity (99.97%) and nanosized spherical α-Al₂O₃ powders with the diameter of 40～50nm and BET surface area 32.5m²·g^-1 can be obtained by calcining AACH at 1150℃ for 1.5h， the sequence of phase transformation during calcination was AACH → amorphous Al₂O₃ → γ-Al₂O₃ → α-Al₂O₃， and the activation energy of AACH decomposition is (115±5)kJ·mol^-1.     

由镁、铝醇盐配合物合成纳米粒子MgAl2O4尖晶石

Mg and Al alkoxide complex was synthesized in a cell without battery separator by electrochemical dissolution of aluminum for 6 h and magnesium for 1.8 h at 45 ℃ in ethanol solution of 0.04 mol·dm^-3 (Bu₄N)Br with a current density of 100 mA·cm^-2. IR and Raman spectroscopy were used to characterize the structure of the precursor of MgAl₂O₄. The results show that the current efficiency attains 98.4% and the precursor is MgAl₂(OCH₂CH₃)₅(acac)₃. The acac^- group-containing precursor could prevent it from agglomeration. The xerogel was obtained by drying in vacuum for 24 h and hydrolysis under pH≈8.5 of the precursor, which was heated at 350 ℃ for 2 h to obtain the nano-MgAl₂O₄ powder. XRD and TEM were used to investigate the structure of nano-MgAl₂O₄. The result suggests that the xerogel with an average particle size of 10 nm and the Nano-sized Spinel MgAl₂O₄ Particle of 12 nm thus obtained are with high purity.     

电镀烧结法制备Ti/SnO2-Sb2O4电极的研究

The Ti/SnO₂-Sb₂O₄ electrode has been prepared by the electroplate-sinter method. The effect of SbCl₃ adding amount and sintering temperature on its electrode lifetime and oxygen evolution potential were investigated by means of EDX, SEM and XRD analysis. The results indicated that the electrode appeared the best performance when the SbCl₃ adding amounts was 0.2g and the sintering temperature was 550℃. In optimized conditions Ti substrate was entirely covered by SnO₂-Sb₂O₄ and the combinations among them were tight. Due to the use of electroplate method, the electrical conductivity, the oxygen evolution potential and the electrode lifetime were increased, so the elec-tro-catalytic activity and the electrochemical stability of the prepared electrode were found to be superior.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

TiO2胶粒在铝合金表面的电泳沉积及所制薄膜的光催化性能研究

TiO₂ membranes were prepared on aluminum-alloy thin plates by electrophoretic deposition and dip coating in a colloid solution of TiO₂, respectively. The photocatalytic activity of TiO₂ membrane was compared using ethylene as reactant, and the crystal and morphological structure of the membrane were characterized by XRD and SEM. The results showed that a more compact membrane with high loading of TiO₂ but lower photocatalytic activity of unit TiO₂ mass was obtained by electrophoresis compared with dip coating method. The addition of polyethylene glycol (PEG) to the sol of TiO₂ could improve the specific photocatalytic activity (ethylene conversion per unit mass TiO₂ and unit area of membrane piece) of the electrophoresis-membrane prepared from the sol, but could not change the specific photocatalytic activity of the dip-coating membrane from the sol. The ethylene conversion on the electrophoresis membrane prepared from the sol containing PEG (50 g·L^-1) was 9 times of that on the dip coating membrane. The effect of PEG on the properties of electrophoresis-membrane of TiO₂ was attributed to the change of electrokinetic properties of sol. Addition of PEG decreased ζ potential value of the sol and the mobility of the sol particle, increased viscidity of the colloid, thus decreasing both the electrophoresis deposition velocity of colloid particles and the electroosmosis velocity of diffuse layer of colloid particles. These favored the formation of a low compact and porous membrane on the electrode in electric field, and thus increasing the availability of TiO₂ in photocatalytic process.     

ZrxTixAl1-2xO2的制备及其在三效催化剂上的应用

Zr_0.5Ti_0.5O₂(ZT) and Zr_0.25Ti_0.25Al_0.5O₂(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption， XRD and NH₃-TPD. The activity of Pt/Zr_0.5Ti_0.5O₂ and Pt/ Zr_0.5Ti_0.5Al_0.5O₂ catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area， larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon， carbon monoxide and nitrogen oxides， especially better conversion for nitrogen oxides (NO_x). The addition of Al₂O₃ into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural， structural， surface acidity and thermal stability.     

Sr3Al2O6∶Eu2+红色发光纳米晶的新型形貌与发光性能的研究

A red luminescent Sr₃Al₂O₆∶Eu²⁺ nanocrystallites with new morphology were synthesized by sol-gel route assisted by microwave irradiation. The phosphor powders were characterized by X-ray diffraction (XRD)， scanning electron microscopy (SEM) and fluorescence spectroscopy. The results reveal that the calcination temperature of the Sr₃Al₂O₆∶Eu²⁺ phosphor crystallites greatly affects its morphology. With temperature increasing， the phosphor crystallites morphology showed primarily from nanorod-like， mixture of nanorod and flower-like to homogeneous flower-like morphology. The effects of new morphology on luminescent properties of phosphors were investigated. Uniformly dispersed flower-like Sr₃Al₂O₆∶Eu²⁺ phosphor powders showed the strongest luminescent intensity and the longest afterglow time.     

正钛酸胶溶法制纳米TiO2薄膜及性能表征

The Nanometer TiO₂ thin film was prepared by sol method with titanic acid precursor from industrial TiOSO₄ solution. The characters of the sol and the factors affecting sol formation were investigated by ζ electricity potential. The crystalline structure, particle size, appearance shape and photo-catalytic activity were characterized by XRD, SEM, TEM and spectrophotometer. The study show: (1) pH value and HNO₃concentration effected importantly on the forming process and stability of the sol. The thermodynamic condition for forming sol is pH=0.5～1.5. The lower the HNO₃concentration,the more stable the sol. The ζ electricity potential of the sol, with 5% HNO₃as gluing reagent, was up to 48 mV, and shelf life of the sol could more than 10 months. (2) The film, made from the sol and crystallized at 400 ℃, had the characters of anatase structure and crystal size of 18.5 nm by XRD analysis. The SEM imagines show that TiO₂ film was with the characteristics of tight surface structure, The TEM imagine showed the mean particle size is about 20 nm. The photo-degrading test data indicate that the photo-degrading rate to methyl orange solution of 20 mg·L^-1 was more than 84% in 5 hours.     

有机体系中纳米TiO2 / ZrO2修饰电极的制备及电催化活性

The complexes Ti(OCH₂CH₂O)₂ and Zr(OCH₂CH₂O)₂ were directly synthesized by using HOCH₂CH₂OH dissolution in 50 mL flask. The nano-ZrO₂ / TiO₂ powders were prepared by a direct sol-gel synthesis using the above solution and followed by drying at 400 ℃ for 2 h. The complexes were characterized by FTIR and ¹H NMR. XRD and TEM were used to investigate the structure of nano-ZrO₂ / TiO₂. The results show that the complexes containing ^-OCH₂CH₂O^- group could prevent the precursor from agglomeration and sintering during the hydrolysis and calcination process. The ZrO₂ / TiO₂ powders of 20～35 nm was thus obtained in a high purity. The highly active nano-ZrO₂ / TiO₂ modified electrode was prepared by using daubing and calcination. The electro-catalytic activities of this electrode in (COOH)₂ were investigated. The discharge current of nano-ZrO₂ / TiO₂ electrode increased obviously. In preparative electrolysis under optimal conditions, the average yield and current efficiency for HOOC-CHO were 84.7% and 91.6 %, respectively.     

Binuclear Aluminum Complexes Supported by Linked Bis(β-diketiminate) Ligands for Ring-Opening Polymerization of Cyclic Esters

Binuclear aluminum alkyl complexes 2a–4g supported by linked bis(β-diketiminate) ligands were synthesized via the reaction of AlEt_3 or AlMe_3 and the corresponding proligand in a 2:1 molar ratio with moderate yields. The isolated complexes were well-characterized by ~1H-NMR, ~(13)C-NMR and elemental analysis. The binuclear nature of aluminum complex 2b was further confirmed by an X-ray diffraction study. All complexes 2a–4g could efficiently initiate the ring-opening polymerization(ROP) of ε-caprolactone in toluene. The substituents at the aromatic rings and the linker unit in the auxiliary ligands exerted significant influence on the catalytic behavior of the investigated aluminum complexes. Complex 4g(R~1 = R~2 = Cl) containing propylenyl bridging unit exhibited the highest catalytic activity among these complexes, which might be attributed to the increased electrophilicity of the metal center as well as more opened coordination sphere. The molecular weights of obtained poly(ε-caprolactone)s deviating considerably from the theoretical values indicated that the ROP of ε-caprolactone by complexes 2a–4g was not well-controlled, which was also judged from the broad molecular weight distributions(MWD = 1.47-2.47) of produced poly(ε-caprolactone)s. These complexes proved to be inactive toward the polymerization of rac-lactide alone. In the presence of alcohol the polymerization occurred, which was actually initiated by the decomposition species of the aluminum complex upon the treatment with isopropanol.     

聚合Al13晶体的制备及表征

近几十年来 , 环境污染的日益严重使人们对健康问题和全球生态系统越来越关注 ?由于一个元素的生物可给性在很大程度上取决于它存在的物理化学形态和浓度 , 准确测定环境和生物体系中的痕量元素的不同形态是研究这些元素的生物毒性 ? 生物有效性和传输机理的关键 ?形态分析成了     

水解聚合铝溶液中Al30形态的研究

水解聚合铝形态一直是分析、催化、土壤、地球化学、新材料、环境科学和生物毒理学等众多领域研究的前沿和热点。Keggin 结构的Al₃₀ 形态是迄今为止发现的电荷最高的水解铝聚合阳离子,具有独特的分子结构和纳米分子尺寸,它对催化化学、新型功能材料、高效絮凝剂的开发以及铝的水解聚合转化规律研究具有重要意义。本文主要论述了Al₃₀形态的形成、形态分析方法、结构模型以及形成机理等方面的最新研究进展,并对水解聚合铝溶液的研究发展趋势进行了展望。     

N2O and NO2 Formation in the Disproportionation of no over Ion Exchanged Cu-ZSM-5 at Lower Temperature

NO₃-type and NO₂-type adsorbed species are formed on Cu-ZSM-5 together with adsorbed O species at 523 K in the decomposition of NO accompanied by the evolution of N2, N₂O, and NO₂. This revised version was published online in June 2006 with corrections to the Cover Date.     

EPR study of the mobility of paramagnetic species on the surface and in the bulk of solids

The temperature dependence of EPR spectra provides information on the mobility of paramagnetic species at the gas (liquid)/solid interface and in the bulk of solids. Changes in the environment of molecules on solid surfaces caused by their motion occurring upon thermal treatment at various temperatures are observed. Superoxide radical can migrate from Co(III) to Mg(II) surface sites of the CoO–MgO solid solutions. In aqueous solutions transition metal ions coordinate water molecules, forming aquacomplexes which are usually free to tumble within the liquid medium. Their mobility is, however, strongly modified in the vicinity of the solid surface or inside the narrow pores. In solids the migration of paramagnetic species from the surface into the bulk is controlled by the temperature of thermal treatment. In the case of V₂O₅–ZrO₂ catalyst this process is strongly influenced by the phase transitions occurring in the solid matrix and by the presence of alkali metals.     

Production of reactive oxygen species induced by a new [60]fullerene derivative bearing a tetrazole unit and its possible biological applications

The wide range of physical and chemical properties of modified fullerenes has drawn increasing attention in the past few years. As part of this research, this paper describes the preparation, characterization, and photophysical properties of a new fullerene derivative chemically modified with a tetrazole. The photophysical properties were studied by EPR radical spin-trapping technique and showed that reactive oxygen species (ROS) can be produced through UVA photosensitization. EPR spin-trapping experiments with singlet oxygen (¹O₂) and superoxide (O₂⁻) inhibitors (β-carotene and superoxide dismutase, respectively) revealed also that: (i) the main ROS produced is ¹O₂ and (ii) ¹O₂ is being partially dismutated to O₂⁻. The results suggest that this derivative can be used in biological applications, as for example, in topic photodynamic therapy (PDT) as a photosensitizer.     

Chromium speciation and preconcentration using zirconium(IV) and zirconium(IV) phosphate chemically immobilized onto silica gel surface using a flow system and F AAS

A procedure for chromium speciation by F AAS using a flow system has been proposed. In this system, Cr(III) and Cr(VI) ions were adsorbed sequentially onto a mini-column packed with silica gel modified with zirconium phosphate and a mini-column packed with silica gel modified with zirconium oxide, respectively. The elution of Cr(III) and Cr(VI) was made with, respectively, nitric acid solution and tris(hydroxymethyl)methylamine (THAM) solution in reverse mode and determination by flame atomic absorption spectrometry without interference of the matrix. Chemical and flow variables as well as concomitant ions were studied in the developed procedure. The enrichment factor for Cr(III) and Cr(VI) was 20.8 and 24.9, respectively, using a preconcentration time of 3.75 min. The limit of detection for Cr(III) and Cr(VI) was 1.9, and 2.3 μg l⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation in solutions containing 100 μg l⁻¹ of chromium species, by analyzing a series of seven replicates, was lower than 3.0%. The accuracy was assessed through recovery experiments of water samples and using another methodology.     

Characterization and separation of Al13 species using gel-filtration chromatography

A polyaluminum chloride (PAC) sample was prepared using a slow alkaline titration method. The Bio-Gel P-100 gel column chromatographic technique was used to separate and characterize the various forms of aluminum present in the prepared PAC solution. The effluents from a gel column were monitored using online chemical method: Al-Ferron timed complexation spectrophotometry and by ²⁷Al nuclear magnetic resonance (NMR) spectroscopy. Effects of different experimental conditions such as eluent flow rate, ionic strength and pH on separation of Al₁₃ were investigated. Experimental results indicated that molecule size exclusion was not the only parameter affecting the column chromatographic separation efficiency of Al₁₃ but molecule charge as well. Reducing the eluent flow rate, increasing the ionic strength and suitable pH resulted in increase in the separation efficiency. Experimental results clearly indicated that by varying the experimental conditions, it is possible to produce pure Al₁₃ species using a gel column chromatographic technique.     

Study on the atmospheric photochemical reaction of CF3 radicals using ultraviolet photoelectron and photoionization mass spectrometer

A study of the atmospheric photochemical reaction of CF₃ radical with CO and O₂ was performed by using a homemade ultraviolet photoelectron spectrometer-photoionization mass spectrometer (PES-PIMS). The electronic structures and mechanism of ionization and dissociation of CF₃OC(O)OOC(O)-OCF₃ were investigated. It was indicated that the two bands on the photoelectron spectrum of CF₃OC(O)OOC(O)OCF₃ are the result of ionization of an electron from a lone pair of oxygen and a fluorine lone pair of CF₃ group. The outermost electrons reside in the oxygen lone pair. The experimental and theoretical first vertical ionization energy is 13.21 and 13.178 eV, respectively, with the PES and OVGF method. They are in good agreement. The photo ionization and dissociation processes were discussed with the help of theoretical calculations and PES-PIMS experiment. After ionization, the parent ions prefer the dissociation of the C—O bond and giving the fragments CF₃OCO⁺ and CF₃⁺. It demonstrated that the ultraviolet photoelectron and photoionization mass spectrometer could be applied widely in the study of atmospheric photochemical reaction. Supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KZCX2-YW-205), Hundred Talents Fund, 973 Program of Ministry of Science and Technology of China (Grant No. 2006CB403701) and the National Natural Science Foundation of China (Grant Nos. 20577052, 20673123)     

Attempts to Exchange Iron into H-Y and H-ZSM-5 Zeolites by in situ Formed Chloride-Containing Mobile Species

Three variants of solid-state ion exchange were studied. Iron exchange was found to proceed in the first case, in theFeCl₂+NH₄ZSM-5 FeZSM-5 + NH₄Cl process, even at low exchange capacity (Si/Al = 25).The second, Fe₂O₃ (hematite) + HZ direct reaction does not result in any noticeable interaction for eitherZ = Y or ZSM-5. This process can significantly be promoted by introducing CCl₄ vapor via forming chlorine-containingmobile species. However, the structure of the Y zeolite largely collapses during this treatment, whereas the crystalline state of ZSM-5is preserved.     

Low coordinate germanium and tin compounds (ArO)2ME and (ArO)2MM′Ln M=Ge, Sn; E=S, Se, –NSiMe3 M′=Cr, W, Fe, Pt [Ar=2,4,6-tris((dimethylamino)methyl)phenyl-]

The reactions of the divalent species (ArO)₂M (Ar=2,4,6-[(CH₃)₂NCH₂]₃C₆H₂; M=Ge, Sn) with either Me₃SiN₃, elemental S₈, Se or transition metal complexes M′(CO)_n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph₃P)₂Pt·C₂H₄ have resulted in the isolation of either the new stable formal metallanimines (ArO)₂M=N–SiMe₃, germanethione, -selone (ArO)₂Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)₂M=M′(CO)_n, (ArO)₂M=Pt(PPh₃)₂ complexes, respectively. The direct oxidation of the (ArO)₂M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)₂M–O–]₂. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)₂Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)₂M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione.