固相配位化学反应研究——ⅩⅩⅩⅩⅠ.[Co(NH_3)_5(H_2O)]Br_3,[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应动力学研究

本文主要用气相色谱逸出气体分析方法,借助于红外、紫外可见漫反射谱等手段研究了[Co(NH_3)_5(H_2O)]Br_3、[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应,计算了失水与失氨的动力学参数,发现第一步反应失水生成一取代中间产物,其活化能与外加阴离子无关,为S_N1过程。第二步失氨反应活化能与中心离子M以及取代基Y有关,当M=Co(Ⅲ)时,反应体系的失氨活化能大小有下列顺序:Cl>Br>Ⅰ(E值分别为187、155、98kJ·mol~(-1)),M=Cr(Ⅲ)时则正好相反:Ⅰ>Br>Cl(E值分别为213、146、79 kJ·mol~(-1))。     

Y2O3:Eu3+纳米线阵列的制备与表征

Y2O3:Eu3+红色荧光粉由于色纯度高、化学性质稳定和量子效率接近100%而广泛用于荧光灯和投影电视等方面.近年来,Y2O3:Eu3+的大量研究工作主要集中于纳米粉末的制备方法及其与体相材料不同的发光特性[1～3].最近,有关Y2O3:Eu3+及其稀土化合物的纳米管、纳米线和纳米带一维材料的制备成为研究热点.Wu Changfeng等[4,5]利用表面活性剂合成了Y2O3 : Eu3+纳米管.激光格位选择激发测试结果表明,Eu3+在纳米管中占据3个不同的格位,其611 nm处的红色发光峰出现了宽化.He Yu等[6]采用水热法及退火处理制备出了Y2O3:Eu3+纳米带,发现Eu3+的发射峰不仅宽化,而且出现了625 nm的新峰.Li Yadong等[7～9]采用水热法制备了稀土氧化物、硫氧化物和氢氧化物等的纳米线和纳米管,并探索了其形成机理,同时发现Y2O3S : yb3+,Er3+具有上转换的性质.     

Homogeneous chemiluminescence system in neutral and near neutral aqueous solution with ClO2 as oxidant and its analytical application

Using ClO₂ as chemiluminescence (CL) oxidant, a novel homogeneous CL system in neutral and near neutral aqueous solution is proposed in this paper. ClO₂ could oxidize sulfite in pH 5.0–8.5 acetate buffer to produce CL emission, and pipemidic acid could sensitize the CL system. The ClO₂–SO₃²⁻–pipemidic acid reaction was used as a model CL system and explored the possibility of highly active and eco-friendly ClO₂ being used as CL oxidant in neutral and near neutral aqueous solution. Combined with flow-injection analysis, the proposed CL system was applied to the automated dissolution testing of pipemidic acid tablet. Compared with the common strong acidic or strong basic CL system, this proposed CL owns its advantages.     

镝(III)与酰腙及1,10菲啰啉多元配合物的晶体结构及荧光性质

在水乙醇混合体系中 ,首次得到 2 羰基丙酸水杨酰腙 (C10 H10 N2 O4) ,1,10 菲啉 (C12 H8N2 ,简写作phen)与Dy(NO3 ) 3 ·3H2 O的配合物 [Dy(C10 H8N2 O4) (phen) (NO3 ) (H2 O) 2 ]·H2 O .该配合物属单斜晶系 ,空间群为P2 1/c,晶胞参数a =1 5 2 4( 3 )nm ,b =1 10 18( 19)nm ,c =1 468( 3 )nm ,β =92 2 8( 2 )° ,V =2 4 63 ( 7)nm3 ,Z =4,μ =3 10 0mm-1,Dc=1 83 1g/cm3 ,F( 0 0 0 ) =13 40 ,R =0 0 3 14 ,wR =0 0 660 ,GOF =0 966.测试结果表明 ,该单晶结构为镝的 9配位配合物 ,其中一个 2 羰基丙酸水杨酰腙分子以羧基氧、酰胺基中的羰基氧和CN中的氮与Dy3 + 三齿配位 ,形成两个稳定的共边五元环 ,一个 1,10 菲啉分子以二齿方式配位、一个硝酸根和两个水分子也同时参与配位 ,在空间呈扭曲的单帽四方反棱柱 ,而在配合物周围还有一个游离的水分子 .发光性能测试表明配合物具有很好的荧光性能     

毛细管电色谱中双电层叠加的研究

通过流动相中电解质浓度对毛细管电色谱柱效能的流动相平均线速度的影响，研究了ＣＥＣ中双电层叠加现象。提出选择合适电解质组成的浓度及在制备色谱柱过程中避免细小和破碎的固定相颗粒进入柱中，以有效地减小双电层叠加作用。     

SO_4~(2-)/TiO_2固体超强酸新制备方法及其对形成邻苯二甲酸二丁酯的催化活性

建立了用钛白粉制备固体超强酸SO42-/TiO2的新方法.考察了超强酸SO42-/TiO2的制备条件对催化邻苯二甲酸酐和正丁醇酯化反应的催化活性的影响.实验表明,以合成的超强酸为催化剂,在160℃反应4h,邻苯二甲酸二丁酯的产率大于99%.     

Synthesis and Crystal Structure of a Novel Three-dimensional Cu(II) Compound {[Cu(2,2''-bipy)(C7H4O5S)(H2O)2]·(H2O}n

The title compound, {[Cu(2,2'-bipy)(C7H4O5S)(H2O)2](H2O}n (2,2'-bipy = 2,2'- bipyridine), was synthesized by the hydrothermal reaction of Cu(NO3)2(3H2O, 2,2'-bipyridine and 2-sulphobenzoic acid, and structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P with a = 9.21(3), b = 10.17(3), c = 10.77(3) (A), α = 77.017(16), β = 89.80(8), γ = 68.46(7)°, V = 911(5) (A)3, Z = 2, (D/s)max = 0.001, Mr = 473.94, Dc = 1.728 g/cm3, μ(MoKα) = 1.365 mm-1, F(000) = 486, the final R = 0.0246 and wR = 0.0628 for 3809 observed reflections with I > 2σ(I). The mononuclear crystal structure extends into a two-dimensional net- work via hydrogen-bonding interactions and a three-dimensional framework is further formed by means of π-π stacking interactions.     

Pd_2(dba)_3/BINAP催化合成1,4-双-(4′-苯胺基苯酰基)苯

以Pd2(dba)3/BINAP催化1,4-双-(4′-溴苯酰基)苯和苯胺反应,合成了1,4-双-(4′-苯胺基苯酰基)苯,其结构经UV,1HNMR,13CNMR和元素分析表征。     

LiCoO_2 electrode/electrolyte interface of Li-ion batteries investigated by electrochemical impedance spectroscopy

The storage behavior and the first delithiation of LiCoO2 electrode in 1 mol/L LiPF6-EC:DMC:DEC elec- trolyte were investigated by electrochemical impedance spectroscopy (EIS). It has found that, along with the increase of storage time, the thickness of SEI film increases, and some organic carbonate lithium compounds are formed due to spontaneous reactions occurring between the LiCoO2 electrode and the electrolyte. When electrode potential is changed from 3.8 to 3.95 V, the reversible breakdown of the resistive SEI film occurs, which is attributed to the reversible dissolution of the SEI film component. With the increase of electrode potential, the thickness of SEI film increases rapidly above 4.2 V, due to overcharge reactions. The inductive loop observed in impedance spectra of the LiCoO2 electrode in Li/LiCoO2 cells is attributed to the formation of a Li1-xCoO2/LiCoO2 concentration cell. Moreover, it has been demonstrated that the lithium-ion insertion-deinsertion in LiCoO2 hosts can be well described by both Langmuir and Frumkin insertion isotherms, and the symmetry factor of charge transfer has been evaluated at 0.5.     

Identification of a chemical indicator of the rupture of 1,4-β-glycosidic bonds of cellulose in an oil-impregnated insulating paper system

In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded (TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with 2-furfuraldehyde, which is the current reference in the domain.