高温固相法合成LiNi1/3Mn1/3Co1/3O2及其性能研究

采用高温固相法合成出层状锂离子电池正极材料LiNi_1/3Mn_1/3Co_1/3O₂。通过XRD、ICP、SEM和电化学测试手段对产物的结构、组成、形貌及电化学性能进行了研究。XRD结果表明此方法合成的LiNi_1/3Mn_1/3Co_1/3O₂具有标准的α-NaFeO₂型层状结构，SEM照片显示颗粒粒径大约在500 nm左右，粒径分布较窄。以20 mA·g^-1电流密度放电，充放电电压在2.8～4.4 V之间，其首次放电比容量为170 mAh·g^-1，40次循环容量保持率为85.3%。进一步加入石墨导电剂后，同样条件下首次放电比容量变为179 mAh·g^-1，50次循环容量保持率为89.6%。容量衰减主要发生在前10次循环。XRD和SEM测试表明循环初期容量衰减的原因是由材料本体结构变化和界面反应共同作用的结果。     

X-射线荧光光谱法测定钛铁中的硅、锰、磷、铝

介绍用X-射线荧光光谱仪测定钛铁中Si、Mn、P、Al含量的方法,通过试验确定了合适的研磨时间、压力和保压时间,用压片法制样,建立了各元素的工作曲线,各元素的测定范围分别为Si3.00%～6.00%,Mn1.00%～3.00%,P0.030%～0.070%,Al5.00%～9.00%。通过强度测量得到测定Si、Mn、P、Al的相对标准偏差分别为0.074%、0.308%、0.383%、0.040%,精密度满足测试要求。将该方法测定结果与化学法比对,准确度满足国家标准方法分析误差的要求。     

Reducing a chemical master equation by invariant manifold methods

We study methods for reducing chemical master equations using the Michaelis-Menten mechanism as an example. The master equation consists of a set of linear ordinary differential equations whose variables are probabilities that the realizable states exist. For a master equation with s(0) initial substrate molecules and e(0) initial enzyme molecules, the manifold can be parametrized by s(0) of the probability variables. Fraser's functional iteration method is found to be difficult to use for master equations of high dimension. Building on the insights gained from Fraser's method, techniques are developed to produce s(0)-dimensional manifolds of larger systems directly from the eigenvectors. We also develop a simple, but surprisingly effective way to generate initial conditions for the reduced models.     

排序集抽样下Inverse Rayleigh分布的Fisher信息量及其在参数估计中的应用

文章分别在简单随机抽样和排序集抽样下研究了Inverse Rayleigh分布中对应样本所含刻度参数θ的Fisher信息量.数值结果表示,同等样本容量的排序集样本比简单随机样本提供更多关于θ的信息.接着分别基于简单随机样本和排序集样本构造了θ的一些优良估计,并对估计结果进行了数值比较.     

Chiral hydroperoxides as oxygen source in the catalytic stereoselective epoxidation of allylic alcohols by sandwich-type polyoxometalates: control of enantioselectivity through a metal-coordinated template

The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM(2)(ZnW(9)O(34))(2)](q)(-) [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)(2)(ZnW(9)O(34))(2)](12-), is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)(2)(ZnW(9)O(34))(2)](12)(-) and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template.     

Does core size matter in the kinetics of ligand exchanges of monolayer-protected Au clusters?

This paper compares the kinetics of exchanges of phenylethanethiolate ligands (PhC2S-) of the monolayer-protected clusters (MPCs) Au(38)(SC2Ph)(24) and Au(140)(SC2Ph)(53) with p-substituted arylthiols (p-X-PhSH), where X = NO(2), Br, CH(3), OCH(3), and OH. First-order rate constants at 293 K for exchange of the first ca. 25% of the ligands on the molecule-like Au(38)(SC2Ph)(24) MPC, measured using (1)H NMR, vary linearly with the in-coming arythiol concentration; ligand exchange is an overall second-order reaction. Remarkably, the second-order rate constants for ligand exchange on Au(38)(SC2Ph)(24) are very close to those of corresponding exchange reactions on the larger nanoparticle Au(140)(SC2Ph)(53) MPCs. These are the first results that quantitatively show that the chemical reactivity of different sized nanocrystals is almost independent of size; presumably, this is because the locus of the initial ligand exchanges is a common kind of site, thought to be the nanocrystal vertexes. The rates of later stages of exchange (beyond ca. 25%) differ for Au(38) and Au(140) cores, the latter being much slower presumably due to its larger terrace-like surface atom content. The reverse exchange reaction was studied for Au(38)(p-X-arylthiolate)(24) MPCs (X = NO(2), Br, and CH(3)), where the in-coming ligand is now phenylethanethiol. Remarkably, the rate constants of both forward and reverse exchanges display identical substituent effects, which implies a concurrent bonding of both in-coming and leaving ligands to the Au core in the rate-determining step, as in an associative mechanism. X = NO(2) gives the fastest rates, and the ratio of forward and reverse rate constants gives an equilibrium constant of K(EQ,PE) = 4.0 that is independent of X.     

Effect of Co-solvent on the Palladium Catalyzed Alkoxycarbonylation of Allyl Bromide in Supercritical CO_2

We have studied the palladium-catalyzed alkoxycarbonylation of allyl bromide in supercritical (sc) CO2 and found the reaction rate in sc CO2 was lower than those in some organic solvents1. The possible reason was the lower solubility of sc CO2 for the palladium catalyst. As an effective approach to improve the solubility of varieties of solutes, cosolvent such as ethanol has been widely used in the sc CO2 extraction2,3. Based on the above consideration, we chose several organic reagents…     

DETECTION OF T_g BY MODULATED DIFFERENTIAL SCANNING CALORIMETRY

The glassy transition of the polyethylene terephthalate (PET) sampleswhich have been subjected to solvent induced crystallization (SINC) was investigated bymodulated differential scanning calorimetry (MDSC) and density measurement. The dif-ferential of heat capacity signal, d C_p/dT from MDSC, was used to monitor the SINCprocess. It reveals that the T_g temperature shifts to higher value with the advancement ofSINC. When the toluene-immersing time was longer (168h), the detection of T_g becomemore difficult, because some smaller peaks emerged at the lower temperatures and theseare explained as the movement of small segments in the amorphous region. These observedresults are due to the morphology and structure introduced by the SINC process.     

Mitochondria-targeted ratiometric fluorescent probes for micropolarity and microviscosity and their applications

Two fluorescent "off-on" probes YYH1 and YYH2 were used for bioimaging mitochondrial polarity and viscosity.     

Matrix-isolation FT-IR spectra and theoretical study of dimethyl sulfate

The preferred conformations of dimethyl sulfate and their vibrational spectra were studied by matrix-isolation FT-IR spectroscopy and theoretical methods (DFT and MP2, with basis sets of different sizes, including the quadruple-zeta, aug-cc-pVQZ basis). Conformer GG (of C2 symmetry and exhibiting OSOC dihedral angles of 74.3 degrees ) was found to be the most stable conformer in both the gaseous phase and isolated in argon. Upon annealing of the matrix, the less stable observed conformer (GT; with C1 symmetry) quickly converts to the GG conformer, with the resulting species being embedded in a matrix-cage which corresponds to the most stable matrix-site for GG form. The highest energy TT conformer, which was assumed to be the most stable conformer in previous studies, is predicted by the calculations to have a relative energy of ca. 10 kJ mol-1 and was not observed in the spectra of the matrix-isolated compound.