含铜MCM-48催化剂上糠醛选择性加氢制糠醇

 以MCM-48为载体,采用新颖的负载方法(有机官能团化法)制备了铜基负载型催化剂. 结果表明,活性组分以较高的负载量均匀地分散在载体MCM-48表面,且负载活性组分后,分子筛的结构未被明显破坏. 本文首次将采用此负载方法制备的铜基MCM-48催化剂用于糠醛选择性加氢制糠醇反应,并得到了较高的活性、稳定性及糠醇选择性,该催化剂可以与商业催化剂相比,具有潜在的工业应用价值. 与一维结构的MCM-41相比,三维孔道结构的MCM-48有效避免了孔堵塞,大大提高了催化剂的稳定性. 引入助剂镧有利于羰基加氢,明显提高了糠醛的转化率. 使用后的催化剂并未被氧化,催化剂失活的主要原因之一是积炭.     

二(三苯基膦)水杨酸铜(Ⅰ)乙醇溶剂配合物的晶体结构

0IntroductionThestudyofcopper?complexesisinvestigatedinmanylaboratories.Amongthereasonsforcarryingouttheinvestigationofsuchspeciesaretheirstructuralfeatures犤1犦,theusefulnessofcopper?compoundsinorganicsyntheses犤2犦andthewell-documentedimpor-tanceofcopper?centersattheactivesitesofanumberofprotein犤3犦.Concerningcopper?carboxy-latesafurtherinterestexists,stemmingfromtheiruseinhomogeheouscatalysedhydrogenation犤4犦.Thecopper?bis(triphenylphosphine)cationisasoft,butflexi-bleacceptorionthatcanacc…     

Ni-Cu/Al2O3催化剂上顺酐液相选择加氢制丁二酸酐反应性能

以Al2O3为载体,采用等体积浸渍法制备了一系列Ni-Cu/Al2O3催化剂,用于顺酐液相加氢反应,并结合低温N2物理吸-脱附、H2程序升温还原、H2程序升温脱附、X射线衍射、CO程序升温表面反应等表征结果,详细考察了催化剂中Cu含量对其催化性能的影响.结果表明,Cu的引入提高了活性组分Ni的分散度,促进了催化剂上C=C的加氢活性;同时,由于Ni-Cu双金属间的相互作用,明显抑制了催化剂表面C=O的加氢.当Cu含量为7％时,催化剂上顺酐加氢定向合成丁二酸酐的活性最高.在210℃,H2压力5.0MPa的条件下反应40min时,顺酐转化率与丁二酸酐选择性均达100％.     

超分子三维氢键网络：{[Cu(phen)3](SO4)(H3PCA)2(8H2O)}的晶体结构

A new complex， {[Cu(phen)₃](SO₄)(H₃PCA)₂(8H₂O)}， was synthesized and structurally characterized by single-crystal X-ray analysis. The complex is composed of copper cations， sulfate anions， 1，10-phenanthroline， protocatechuic acid and lattice water molecules. The structure of H₃PCA， SO₄^2- and waters comprises packing of anionic three-dimensional network by hydrogen bonds with cavities. The complex can be considered as a model of host/guest supramolecule. The three-dimensional hydrogen-bonding network is the host species. The Cu(phen)₃²⁺ cations， guest species， occupied the cavities of the host. And the results demonstrate that the form of protocatechuic acid at pH< 1 should be free ligand. CCDC： 191733.     

石墨对铜基自润滑材料高温摩擦磨损性能的影响

通过基体多元合金化和选用不同粒度的石墨颗粒,采用常规粉末冶金方法制备了铜基石墨固体自润滑材料,在大越式OAT-U型摩擦磨损试验机上考察了复合材料从室温到500℃温度条件下的摩擦磨损性能,利用扫描电子显微镜观察分析磨损表面形貌,进而探讨其摩擦磨损机理.结果表明:在室温条件下,石墨颗粒越小,则复合材料的摩擦系数越小,减摩自润滑效果越好;在室温至500℃条件下,选用合适的石墨粒度(0.3～0.5mm)和多元基体合金化,可使铜基石墨固体自润滑材料保持较好的自润滑特性.     

Li＋在PC＋DMF混合溶剂中优先溶剂化的13C NMR研究

利用¹³C NMR光谱技术研究了Li^＋在碳酸丙烯酯(PC)＋N,N-二甲基甲酰胺(DMF)混合溶剂中的优先溶剂化现象. 根据溶剂分子中碳原子的化学位移随锂盐浓度的变化关系, 确定了与Li^＋发生配位的原子. 碳原子的配位位移值随混合溶剂组成的变化关系表明, 在LiClO₄＋PC＋DMF混合物中, DMF分子对Li^＋的溶剂化作用较PC分子强. 定量计算得到, 在n(PC)∶n(DMF)＝1∶1(摩尔比)的混合溶剂中, PC与DMF分子数在Li^＋第一溶剂化层中的比率为0.12, 说明Li^＋优先被DMF分子溶剂化.     

电感耦合等离子体质谱(ICP-MS)法测定土壤中的碘

通过电感耦合等离子体质谱法(ICP-MS)测定土壤中的碘。样品预处理采用艾斯卡试剂熔融、热水提取和阳离子树脂静态交换,试验加入了不同剂量的阳离子交换树脂在不同程度上降低了溶液中Na+ 和Zn2+^{等阳离子的盐效应干扰。研究了乙醇在}ICP-MS中对碘元素的增强效应,用3%的氨水溶液清洗进样系统,有效减少的碘的记忆效应和清洗时间。该方法线性范围宽,方法灵敏度高,检出限低,试剂用量少,环境友好。对苏州及周边区域若干非污染土壤点位进行采样、制备和测试,碘平均含量为2.7μg.g_-1^;同步测试国家有证标准物质,精密度和准确度良好。     

三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能

在水热条件下,通过Wells-Dawson型多酸[As_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(4-吡啶基)-1H-四氮唑(4-ptz)的反应,在同一反应釜中合成出2个结构完全不同的、都包含三核铜簇的多酸基化合物[Cu3(4-ptz)4(H_2O)7(As_2W_(18)O_(62))]·42H_2O(1)和[Cu3(4-ptz)5(H_2O)5(As_2W_(18)O_(62))]·47H_2O(2);当我们以另一种Wells-Dawson型多酸[P_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(3-吡啶基)-1H-四氮唑(3-ptz)反应,获得了另一种多酸基三核铜簇化合物[Cu3(3-ptz)4(H_2O)8(P_2W_(18)O_(62))]·33H_2O(3)。X射线单晶衍射结果表明,化合物1为多酸单支撑三核铜簇的悬臂式结构,化合物2的多阴离子被三核铜簇交替连接形成一维链式结构,而化合物3为多阴离子和三核铜簇形成的孤立结构。吡啶-四氮唑类配体(3-ptz和4-ptz)是形成化合物1~3中三核铜簇的重要结构因素。同时,研究了3个化合物的电化学以及光催化性能。     

Macrocyclic 14-Membered Ring Diketal Dilactams: Evaluation of their Divalent Cation Binding Properties

The binding abilities of a new class of 14-membered ring ligands bearing diketal dilactam functions were explored by UV-visible spectrophotometry. Their formation constants, determined in THF solution, showed appreciable complexation with divalent cations (stability order: Sr²⁺≥Ca²⁺>Zn²⁺≥Mg²⁺>Ba²⁺) whereas no association was observed with monovalent cations. The stoichiometry of the complexes formed was essentially 1:1 although sometimes a low percentage (<10%) of 1:2 (cation–ligand) species was detected. The corresponding formation constants determined by computation (STAR program) were in the range 1.5<log?β ¹¹<4.8 and 4.4<log?β ¹²<7.1. They depend significantly on the nature of the substituents. In addition, solvent extractions carried out in a water–chloroform system showed the highest constants (log K ^ex) for the most substituted macrocycles 7b and 7c (norephedrine series) with a lipophilic skeleton.     

The synthesis and fluorescence properties of novel chromenone-crown ethers

o-Dihyroxy-3-phenylchromenone derivatives, namely, 6,7-dihydroxy-3-(3′,4′-dimethoxyphenyl)chromenone and 6,7-dimethoxy-3-(3′,4′-dihydroxyphenyl)chromenone, were obtained from 2,4,5-trihydroxybenzaldehyde/3,4-dimethoxyphenylacetic acid and 2-hydroxy-4,5-dimethoxybenzaldehyde/3,4-dihydroxyphenylacetic acid, respectively, in the presence of acetic anhydride and sodium acetate under an inert atmosphere, after treatment with MeOH/HCl(aq). The chromenone-crown ethers were prepared from cyclic condensation of o-dihydroxy-3-phenylchromenones with poly(ethylene glycol) ditosylates in the presence of CH₃CN/alkali metal carbonates. The chromatographically purified novel chromenone-crown ethers were identified by ¹H NMR, MALDI-TOF mass spectrometry and elemental analysis. The fluorescence and UV–vis spectroscopic properties of the obtained chromenone-crown ethers and their complexes with Li⁺, Na⁺ and K⁺ perchlorate salts were estimated in acetonitrile. The quantum yields of novel chromenone-crown ethers were determined by the comparative method.