Syntheses,magnetic properties,and reactivity of dinuclear oxovanadium (IV) and copper (II) complexes with (μ-diphenylphosphinato)-bridges

Novel dinuclear oxovanadium (IV) complexes having the formula [(VO)₂(dpp)₃(bpy)₂]NO₃·2H₂O (1), [(VO)₂(dpp)₃(phen)₂]-NO₃·H₂O (2), [(VO)₂(bmp)₃(bpy)₂]NO₃·H₂O (3), and [(VO)₂(bmp)₃(phen)₂]NO₃·H₂O (4), and copper (II) complexes having the formula [Cu₂(bmp)₂(phen)₂](NO₃)₂·MeOH·H₂O (5), and [Cu₂(bmp)₂(bpy)₂](NO₃)₂ (6) (where Hdpp=diphenylphosphinic acid, Hbmp=bis(4-methoxyphenyl)phosphinic acid, bpy=2,2^′-bipyridine, and phen=1,10-phenanthroline) with (μ-phosphinato)-bridges, 1–6, have been prepared and characterized. Crystal structure of complex 2 reveals that two vanadium ions are linked by tris(μ-phosphinato)-bridges. The magnetic susceptibility data for 1–3, and 6 conform to the usual dimer equation with −2J values of 16–24 cm⁻¹, indicating a weak antiferromagnetic interaction between vanadium(IV) ions.The oxidation of cinnamyl alcohol was studied using complexes 1–6 as catalyst and molecular oxygen as an oxidant. In the presence of complex 3 as a catalyst, cinnamyl alcohol was oxidized to cinnamaldehyde 61% yield in 7 h. Consequently, complex 3 activates oxygen, and then alcohol was quite efficiently oxidized by activated oxygen.     

(K,Na) (Nb,Ta,Sb)O3粉体制备及陶瓷介电性能研究

Ta/Sb掺杂的K0.5Na0.5Nb0.7TaxSb0.3-xO3(KNNSTx,x＝0.06,0.09,0.12,0.15,0.18,0.21, 0.24)粉体经水热合成,Ta、Sb对粉体物相、微观结构的影响被系统研究,烧结后陶瓷的微观结构、介电性能表明:陶瓷物相均具有纯钙钛矿结构;随着Ta含量的增加陶瓷晶粒尺寸逐渐增大,x＝0.09、0.12时较小粒径颗粒均匀分布在大颗粒的空隙之间,陶瓷密度增加;样品的介电常数随着Ta含量的增加x＝0.06～0.12逐渐降低,x＝0.15～0.24逐渐增加,居里温度均在350 ℃左右,且x＝0.09、0.12时陶瓷介电损耗较小.     

加热炉(F1101,F1102, 1203,F1501)

(一)概述(1)石脑油过热炉(F1101)作予脱硫石脑油加热用,即石脑油+弛放气混合经 E1101 A,B,C,D 四组热交换器后,使温度达310℃,进入加热炉使其过热到380℃送第一Co—Mo 加氢反应     

亚砷酸钠(偏亚砷酸钠,NaAsO_2)

正1)性质。工业品亚砷酸钠不是单一组分,它是由偏亚砷酸钠(NaAsO_2)、三氧化二砷(As_2O_3)、正亚砷酸钠(Na_3AsO_3)、酸式亚砷酸钠(Na_2HAsO_3)等组成,但其基本分子式可以写成NaAsO_2,也可以用NaAsO_2·nAs_2O_3表示,其中0.305n0.34。工业品亚砷酸钠中偏亚砷酸钠约占65%(质量分数),游离白砒霜(As_2O_3)约占31%(质量分数),但两者并不是机械的混合,而是以化合物的形态出现。亚砷酸钠为白色粉末,但为了     

Influence of Al-substitution on structures,resistivity and magnetic properties of LaxSr(2−x)Fe(1+y)Mo(1−y)O6 (x=3y,y=0.05, 0.1, 0.15, 0.2)

Two series of single-phased La_xSr_(2−x)Fe_(1+y)Mo_(1−y)O₆ and La_xSr_(2−x)Fe_(1+0.5y)Al_0.5yMo_(1−y)O₆ (x=3y, y=0.05, 0.1, 0.15 and 0.2) double perovskites were prepared by solid-state reaction. The effects of Al-substitution on the structures, resistivity and magnetic properties of La_xSr_(2−x)Fe_(1+y)Mo_(1−y)O₆ were investigated. Although Al-replacement exhibits a negligible influence of on the B-site ordering degree, it results in the suppression of magnetisation caused by non-magnetic Al³⁺ ions. Reduction of grain sizes leads to increased resistivity, thus an optimised magnetoresistance (MR) behaviour is observed. The greatest MR extent improvement can be obtained when y is 0.15 and the MR% of the Al-doped ceramics reaches −10.5% (10 K, 1 T), which is 2 times greater than that of the undoped ceramics (−4.6%, 10 K, 1 T). Interestingly, the Curie temperature (Tc) of both Al-doped and undoped samples maintained relatively constant values of approximately 420 K and 405 K, respectively, which were different results from the data obtained for similar electron-doping systems in the literature.     

Effect of functionlization of N,N-dibenzyldithiocarbamate: synthesis,spectral and structural studies on bis(N-benzyl-N-(4-methoxybenzyl)dithiocarbamato-S,S′)zinc(II) and bis(N-benzyl-N-(4-cholrobenzyl)dithiocarbamato-S,S′)cadmium(II) and their use for the preparation of MS (M = Zn,Cd)

Bis(N-benzyl-N-(4-methoxybenzyl)dithiocarbamato-S,S′)zinc(II) (1) and bis(N-benzyl-N-(4-chlorobenzyl)dithiocarbamato-S,S′)cadmium(II) (2) have been prepared and characterized by elemental analysis, IR and NMR (¹H and ¹³C) spectroscopy and single-crystal X-ray analysis. Complexes 1 and 2 exist as monomer and dimer, respectively. Crystal structures of 1 and 2 confirm the presence of four coordinated zinc in a distorted tetrahedral arrangement and five coordinated cadmium in a distorted square pyramid arrangement, respectively. Both the complexes are further stabilized by various interactions such as C–H···S, C–H···N, C–H···O and C–H···π (chelate). C–H···O interaction leads to the formation of dimer in complex 1. In complex 2, C–H···π (chelate) interaction runs in opposite directions which results in the polymeric chain. ZnS and CdS have been prepared from 1 and 2, respectively, and characterized by powder X-ray diffraction, SEM, UV–Vis and fluorescence spectroscopy. The X-ray diffraction pattern confirms the wurtzite phase of as-prepared ZnS and CdS.     

线形聚(D,L-乳酸)和星形聚(D,L-乳酸)的合成研究

在辛酸亚锡Sn(Oct)₂催化下，分别用丙炔醇和季戊四醇引发D,L-丙交酯(DLLA)的开环聚合(ROP),合成了具有末端炔基的线形聚(D,L-乳酸)(PDLLA)和四臂星形聚(D,L-乳酸)(S-(PDLLA)₄),通过核磁共振氢谱(¹H NMR)和凝胶渗透色谱(GPC)对聚合物的结构和相对分子质量进行了表征。合成产物可用于后续制备基于聚乳酸的两亲性嵌段共聚物，为生物可降解性高分子材料的开发应用提供实验依据。     

M_(0.5)Co_(2.5)O_4(M=La,Ce,Pr,Nd)尖晶石型复合氧化物催化剂催化分解N_2O性能

采用共沉淀法制备了M_(0.5)Co_(2.5)O_4(M=La,Ce,Pr,Nd)钴基尖晶石型复合氧化物催化剂,运用XRD、SEM、H_2-TPR和O_2-TPD-TG等对催化剂物化性能进行表征,并在固定床微型反应器中评价催化剂催化分解N_2O性能。结果表明,稀土金属掺杂改性的钴基尖晶石型复合氧化物催化剂粒径明显减小,比表面积增加,氧化还原性能得到改善,催化分解N_2O活性提高,其中,M_(0.5)Co_(2.5)O_4催化剂催化分解N2O温度低,T10和T95分别为342℃和499℃。     

层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(1.95)Y_(0.05)(Y=O,F,Cl,Br)正极材料的合成及高温电化学性能研究

采用溶胶-凝胶法合成层状LiNi1/3Co1/3Mn1/3O1.95Y0.05(Y=O,F,Cl,Br)正极材料,在850℃空气氛围下煅烧20h得到晶型较好的正极材料。以XRD、SEM和充放电测试等手段对材料的晶体结构、表观形貌和电化学性能进行表征。XRD显示F-和Cl-掺杂材料具有高度有序的二维层状结构;充放电测试表明,掺杂F-和Cl-的材料放电比容量、循环性能和倍率性能均优于未掺杂材料,特别是掺杂F-材料在55℃,电压范围为2.0～4.6V,0.15mA电流下首次放电比容量高达207.5mAh/g,且0.9mA电流下第60次循环的容量仍达到165.1mAh/g。掺杂Br-的材料结构稳定性、循环性能和放电比容量均比未掺杂材料差。     

20%BaCO_3/La_(0.8)Sr_(0.2)MO_3(M=Fe,Co,Mn)催化分解NO的研究

通过NO程序升温吸附脱附(NO-TPD)分析测试手段,研究了20%BaCO3/La0.8Sr0.2MO3(M=Fe、Co、Mn)催化分解NO的机理,解释La0.8Sr0.2MO3(M=Fe、Co、Mn)与BaCO3简单混合后催化分解NO的性能提升的原因。     

Synthesis,characterization and crystal structure of (cis-P,P′-diphenyl-1,4-diphospha-cyclohexane)molybdenum(0)tetracarbonyl

The preparation of the novel (cis-P,P′-diphenyl-1,4-diphospha-cyclohexane)molybdenum(0)tetracarbonyl complex is described. The spectral data and X-ray structure of the title complex are reported. The results of the crystallographic work show a distorted octahedral complex around the metal center, the first of its kind reported for the P,P′-diphenyl-1,4-diphospha-cyclohexane ligand.     

Zr_(0.9)Ti_(0.1)(Ni,Co,Mn,V)_(2+α)贮氢合金的制备过程对其性能的影响

测定了Zr_(0.9)Ti_(0.1)-Ni,Co,Mn,V)2+( 贮氢合金在铸态、快淬态及快淬合金经不同退火温度处理后的压力(组成(温度曲线，计算了它们的焓变值，测试了其电化学容量. 结果表明：快淬后的贮氢合金随退火温度的增加，焓变值和放电容量也增加. 在1173 K温度下退火处理的贮氢合金，其放电容量(379 mA(h/g)较铸态合金好，但它的活化性能不如铸态合金.     

探索创新(青瓷雕塑,创作漫谈)

宜兴青瓷,历史悠久,具有独特的民族风格.远自商周,就有原始的青瓷生产,经春秋到南北朝已有大量的烧造.到了唐代,宜兴青瓷无论在数量上、造型、装饰、原料配方、和烧成技术上等都有明显的进步.宜兴涧?唐窑的发掘,证明它是我国至今保留烧制青瓷,最早最完整的青瓷窑.宜兴青瓷,前后经历大约一千七百多年的发展,到宋以后,由于种种原因,至使宜兴青瓷逐渐衰落,以至中断、失传.从发掘的古代宜兴青瓷雕塑中,以青狮(辟邪)、神兽罐等为代表,其它雕塑品种不多,大量的是日用器皿用具.解放后,在中国共产党和毛主席的领导下,经历二十多年的努力,宜兴青瓷得到了恢复,并有了新的发展.青瓷雕塑不断探索、创新,打开销路,争取出口以及进入美国市场,开创了另一个新局面.青瓷雕塑总的分两大类:一是独立的雕塑——陈设品;一是雕塑和使用相结合的——工艺品.     

Cyano-Bridged Heteropolynuclear Ni(II), Cu(II) and Cd(II) Complexes, [M(deten)2Ni(μ-CN)2(CN)2] n

Three new complexes [M(deten)₂Ni(μ-CN)₂(CN)₂] _n (M = Ni, Cu and Cd, deten = N,N-diethylethylenediamine) have been synthesized and characterized by chemical, thermal analysis, FT-IR and Raman spectroscopies. The crystal structure of the Cd complex has been determined by X-ray single crystal diffraction. Structural study reveals that the Ni²⁺ and Cd²⁺ ions are located on inversion centers, and adopt slightly distorted square-planar and octahedral geometries, respectively. In the crystal structure, the intermolecular N–H⋯N hydrogen bonds link the polymeric chains into a two dimensional network. Vibrational spectral data indicate the presence of two ν(C≡N) for complexes can be assigned to the terminal and bridging cyanides. The decomposition reaction take places in the temperature range 30–1000 °C in the static air atmosphere.     

ZnO∶Al包覆CaSiO_3∶(Pb,Mn)荧光粉(英文)

利用溶液中的共沉淀反应制备了CaSiO3∶(Pb,Mn)红色光致荧光粉。以Zn(NO3)2·6H2O和AlCl3·6H2O为原料,借助CO(NH2)2水解反应,用化学均相共沉淀法和热处理工艺在荧光粉表面包覆一层ZnO∶Al透明导电薄膜。对包覆前后的样品进行了X射线衍射结构分析、光致荧光分析、透射电镜形貌观察及电阻测量。结果显示:包覆后荧光粉的电导率显著提高,但光致荧光峰的位置和强度无明显变化。综合考虑包覆对荧光粉电阻率和荧光性质的影响,优化包覆条件和热处理条件为:n(Zn)/n(Ca)=10%,n(Al)/n(Zn)=5%,75℃水解1.5h;包覆后的样品在500℃热处理45min。     

A cyanohydridoborato–vanadium(II) complex,trans-[V(NCBH3)2(thf)4]

[V(NCBH₃)₂(thf)₄], the first cyanohydroborato complex of an early transition metal, has been generated in the system [V(CO)₆]⁻/I₂/tolane/Na[NCBH₃] in THF. The crystal structure reveals an ideal trans configuration (point group D_2h) with about linear CNBH₃⁻ units, and without intermolecular (hydrogen bonding) interactions.     

双标记尿嘧啶核苷-(~(13)C,~(15)N_2)的合成研究

设计了以无水苯为溶剂,双标记尿素-(~(13)C,~(15)N_2)和丙炔酸为原料进行环化反应,粗品经脱色和重结晶后得到双标记尿嘧啶-(~(13)C,~(15)N_2)。在Ar气氛下,双标记尿嘧啶-(~(13)C,~(15)N_2)和1-乙酰氧基-2,3,5-三苯甲酰氧基-β-D-呋喃核糖反应,经处理后得到的中间体1-(2,3,5-三苯甲酰氧基-β-D-呋喃核糖基)尿嘧啶-(~(13)C,~(15)N_2)用氨水水解,即可得到双标记尿嘧啶核苷-(~(13)C,~(15)N_2)。该方法操作简单,中间体只需简单纯化,各步反应收率高,并且~(13)C、~(15)N同位素丰度不被稀释。产物经高效液相色谱法(HPLC)、MS、~1H NMR和~(13)C NMR表征,结果表明,双标记尿嘧啶核苷-(~(13)C,~(15)N_2)质量分数98%,~(15)N同位素丰度98%,~(13)C同位素丰度98%。     

Synthesis,spectral, structural,Hirshfeld surface and DFT studies on bis(N-(4-fluorobenzyl)-N-(2-phenylethyl)dithiocarbamato-S,S′)zinc(II) and its use for the preparation of ZnS and ZnO nanoparticles

Two new complexes, bis(N-(2-phenylethyl)-N-(4-fluorobenzyl)dithiocarbamato-S,S′)zinc(II) (1) and bis(N-(2-phenylethyl)-N-(4-chlorobenzyl)dithiocarbamato-S,S′)zinc(II) (2), have been synthesized and characterized by various physicochemical techniques. Structure of 1 has been determined by single crystal X-ray diffraction. Complex 1 is a dimer. Zinc atom is four coordinated with a distorted tetrahedral environment. Geometry optimization, geometrical parameters, molecular electrostatic potential (MEPs) and frontier molecular orbital analysis of dimeric and monomeric structures of 1 have been carried out by DFT methods and compared with the experimental X-ray diffraction data. The noncovalent interactions in the complex 1 have been analyzed using Hirshfeld surface analysis. 1 and 2 have been used as single source precursors for the preparation of zinc sulfide and zinc oxide nanoparticles. As-prepared zinc sulfides and zinc oxides have been characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), UV–vis absorption, photoluminence and energy dispersive X-ray spectroscopy (EDS). X-ray diffraction study reveals that zinc sulfides and zinc oxides are composed of rhombohedral and hexagonal phases, respectively. Photocatalytic activities of zinc sulfides and zinc oxides were evaluated by degradation of rhodamine B in aqueous solution under UV light irradiation. The results demonstrated the capability of zinc sulfides and zinc oxides as photocatalyst under UV irradiation to degrade the dye.     

Synthesis,structure, and properties of two novel copper(II) complexes, [Cu(phen)(L)2]·6H2O and [Cu(phen)3]·(ClO4)2

Two novel copper(II) complexes, namely [Cu(phen)(L)₂]·6H₂O (1) and [Cu(phen)₃]·(ClO₄)₂ (2) have been synthesized under mild condition (HL = 5-methyl-1H-pyrazole-3-carboxylic acid, phen = 1,10-phenanthroline). We report the structural evidence of discrete water decamer conformation in the solid state. These units are found to act as supramolecular glue in the aggregation of mononuclear copper(II) complex to give a three-dimensional network through hydrogen-bonding. The preliminary investigation on the thermal behavior and the anion exchange property of the complexes are presented.