锌镀层表面有机膦合钼聚多酸盐转化膜的研究

锌镀层表面有机膦合钼聚多酸盐转化膜的研究王济奎方景礼（南京化工大学应用化学系南京２１０００９）（南京大学应用化学研究所南京）关键词锌镀层，有机膦合钼聚多酸盐，转化膜钼酸盐和１－羟基乙－１，１二膦酸（ＨＥＤＰ，）均为被膜型缓蚀剂，可用于金属表面的钝化处...     

Keggin结构稀土钼钒磷四元杂多配合物的合成,表征及苯酚？…

合成了５种通式为（ＮＨ４）１５「ＲＥ（ＰＭｌ９Ｖ２Ｏ３９）２」．ｘＨ２Ｏ（ＲＥ＝Ｌａ＾３＋,Ｃｅ＾３＋,Ｇｄ＾３＋,Ｙ＾３＋,Ｙｂ＾３＋）的稀土钼钒磷四元杂多配合物,并用ＩＲ,ＵＶ,ＸＲＤ,ＩＣＰ,ＴＧ－ＤＴＡ和ＣＶ等手段对其结构和性能进行了表征。催化活性实验表明,标题化合物对苯酚过化羟化制苯二酚反应有良好的催化活性。     

体相及SiO2负载磷钼杂多酸铜盐的性质

采用ＴＧ－ＤＴＡ、ＦＴ－ＩＲ、ＸＲＤ、ＢＥＴ比表面积等方法,研究了体相及ＳｉＯ２负载磷钼杂多酸铜盐的性质,并与磷钼酸作了对比。结果表明,磷钼酸铜盐的热稳定性稍高于磷钼酸,且铜盐的部分结晶水更稳定;但是它们的最后分解产物相同。ＳｉＯ２负载的磷钼酸铜盐以非晶形态高度分散在ＳｉＯ２表面,但它们确实保持了Ｋｅｇｇｉｎ结构,热稳定性也提高约４５℃。     

磷的光化学分析新方法研究

在０．２ｍｏｌ／ＬＨ２ＳＯ４－１０％乙醇介质中及紫外光照射条件下磷钼杂我酸光还原为磷钼蓝，据此建立了一个测定０．０５－２．０μｇ／ｍｌ的光化学分析新方法，并用于度样分析，探讨了光化学反应机理。     

中心原子对Keggin结构杂多钼酸盐氧化还原特性的影响

用电化学方法研究了Keggin结构的砷钼酸盐、磷钼酸盐和硅钼酸盐的氧化还原性质.由实验结果得出中心原子砷、磷和硅对该类杂多钼酸盐氧化还原性质的影响规律。     

新型层状结构磷钼酸盐的水热合成与表征

新型层状结构磷钼酸盐的水热合成与表征于龙，黄晓威（辽宁大学化学系，沈阳１１００３６）微孔晶体材料领域由于磷酸铝，磷酸镓，磷酸铍等新型微孔晶体的合成而得到极大的拓展。磷钼酸盐除可以形成具有经典结构（如Ｋｅｇｇｉｎ结构）的杂多酸型阴离子骨架外。近来又发现...     

微量元素钼的测定和钼酸锂的缓蚀研究

用ＥＤＴＡ滴定法测定了钼酸盐中的钼含量，用重量法研究了钼酸锂对炭钢的缓蚀能力，结果表明，当ＰＨ４时，０．０２－０．０７％钼酸锂对Ａ３钢片的缓蚀力为３６－７４．８％。     

掺杂磷钼酸根离子聚吡咯膜电极对磷钼酸根离子电位响应的研究

用循环伏安法研究了制备掺杂磷钼根离子聚吡咯化学修饰电极的条件，对其性能进行了电化学表征，电极对磷钼酸根（ＰＭｏ１２Ｏ＾３－４０）离子具有选择性电位响应，线性范围为１．０×１０＾－６～１．０×１０＾－３ｍｏｌ／Ｌ。斜率约为５０ｍＶ，测定了电极的有关性能参数。电极可用于无机磷含量的检测。     

钒钼黄分光光度法测定有机化合物中的微量磷

介绍了钒钼黄分光光度法测定有机化合物中微量磷的方法。有机磷经浓硫酸-硝酸氧化分解,转化为正磷酸。在一定酸度下,溶液中的磷与偏钒酸盐和钼酸盐作用,形成稳定的黄色三元杂多酸钒钼磷酸,再用分光光度法测定磷含量。     

二氧化碳与丙烯直接合成甲基丙烯酸用CuPMo／TiO2催化剂的研究

 用溶胶－凝胶法以磷钼酸（MPA）的铜盐溶液水解钛酸四丁酯制备了CuPMo／TiO2催化剂，并用ICP，XRD，TG－DTA，IR，TPD－MS和微反技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化性能．结果表明：杂多钼酸盐与TiO2表面通过O2－桥发生键联．在623K下，杂多阴离子仍保持其原有的Keggin结构；CO2在Lewis酸位Cu（Ⅱ）和Lewis碱位Cu－O－Mo桥氧的协同作用下形成卧式吸附态Cu（Ⅱ）←O－（CO）←（O－－Cu）；丙烯以分子吸附态在催化剂上吸附；在空速1500h－1，压力1MPa和温度563K的反应条件下，丙烯的转化率为4．2％，甲基丙烯酸的选择性为96％．     

磷钨酸插层Zn/Al类水滑石催化合成邻苯二甲酸二(2-乙基)己酯

以对苯二甲酸根阴离子为预支撑体,制备了磷钨酸插层Zn/Al类水滑石杂化物催化剂,将其用于邻苯二甲酸二(2-乙基)己酯(DOP)的合成反应.研究了原料配比、催化剂用量、反应温度、反应时间等对邻苯二甲酸酐转化率的影响,及催化剂的可重复利用性.结果表明,磷钨酸-Zn/Al类水滑石杂化催化剂对DOP合成的催化效果较好,在催化剂用量为苯酐质量的0.76%,异辛醇与邻苯二甲酸酐的摩尔比为2.5,反应温度为180℃,反应时间为4.5 h,带水剂环己烷约为苯酐质量65%的反应条件下,苯酐转化率可达92.8%;反应10 h转化率可达97.9%.催化剂重复使用时转化率略有下降,经过乙醇洗涤再生,活性即可基本恢复.     

SO_4~(2-)/ZrO_2超强酸催化合成邻苯二甲酸二辛酯初探

初步探索了SO42-／ZrO2超强酸作为合成邻苯二甲酸二辛酯（DOP）催化剂的催化性能．详细考察了反应温度、催化剂用量和反应时间对邻苯二甲酸酐转化率的影响．结果表明，反应温度低于428K时，温度的升高显著增加邻苯二甲酸酐的转化率，反应温度高于428K时，温度的升高对转化率的影响较小；催化剂用量为邻苯二甲酸酐的3％时，邻苯二甲酸酐的转化率即可达到93．6％，表明SO42-／ZrO2超强酸催化剂具有很高的催化活性；催化剂使用20小时后，转化率由958％下降到86．5％，表明初步制得的催化剂稳定性还较差；用SO42-／ZrO2超强酸催化剂会成的DOP为无色透明油状液体。其品质明显优于用对甲苯磺酸或液体改作催化剂时的产品。     

SO4^2—／Al2O3固体酸对邻苯二甲酸二辛酯的催化作用

采用固体超强酸催化剂由苯酐与2－乙基己醇通过酯化反应合成邻苯二甲酸二辛酯（DOP）。该固体酸由Al2O3和浓硫酸复配而成，对非均相催化过程具有很高的活性和选择性。考察了工艺条件对转化率的影响。发现用0.2%(wt)-0.3%（wt)超强酸催化剂，转化率接近100％。     

SO2-4/Al2O3固体酸对邻苯二甲酸二辛酯的催化作用

采用固体超强酸催化剂由苯酐与2-乙基己醇通过酯化反应合成邻苯二甲酸二辛酯(DOP).该固体酸由Al2O3和浓硫酸复配而成,对非均相催化过程具有很高的活性和选择性.考察了工艺条件对转化率的影响.发现用0.2%(wt)～0.3%(wt)超强酸催化剂,转化率接近100%.     

Kinetics,mass transfer,and thermodynamic and statistical modeling study for esterification of valeric acid with n‐butanol: Homogeneous and heterogeneous catalysis

The esterification of valeric acid with n‐butanol was studied with homogeneous and heterogeneous catalysts. The activity and performance of homogeneous p‐toluenesulfonic acid and heterogeneous cation exchange resin catalysts Amberlyst 36, Indion 190, and Amberlite IRC‐50 were evaluated. The pseudo‐homogeneous kinetic model was used to investigate the kinetic parameters of homogeneous‐ and heterogeneous‐catalyzed esterification. The UNIFAC (universal functional activity coefficient) approach was used to study the nonideality of the esterification reaction. The reaction was statistically modeled and optimized by the application of response surface methodology. The effects of independent variables such as reaction temperature, initial molar ratio, and catalyst loading on the conversion of valeric acid were investigated. The optimized conditions for the esterification reaction catalyzed by Amberlyst‐36 were found as temperature 360.4 K, initial molar ratio 3.8, and catalyst loading 6.7 wt%. The predicted conversion (89%) at these optimized conditions is in good agreement with the experimental conversion (87.3 ± 1.6%).     

CuO-La_2O_3/AC催化剂上气相合成碳酸二甲酯的研究(英文)

制备出了用于甲醇气相氧化羰基化合成碳酸二甲酯反应的负载铜基催化剂ＣｕＯ－Ｌａ_2Ｏ_3／ＡＣ。考察了预处理的活性炭载体对反应性能的影响。采用ＸＰＳ技术表征了催化剂的表面性质。结果表明,ＣｕＯ－Ｌａ２Ｏ３／ＡＣ催化剂具有催化合成碳酸二甲酯的反应活性：反应性能依赖于催化剂表面的ＣｕＯ和Ｃｕ２Ｏ物种;用盐酸预处理的活性炭载体可明显提高催化剂的活性和稳定性。     

Homo- and heterogeneous Ru-based metathesis catalysts in cross-metathesis of 15-allylestrone—towards 17β-hydroxysteroid dehydrogenase type 1 inhibitors

The cross-metathesis of allylestrone with acrylic acid derivatives using homogeneous and heterogenized Ru-catalysts was evaluated for the synthesis of a new 17β-hydroxysteroid dehydrogenase type 1 inhibitor. Hoveyda-type catalyst containing an additional diethylamino group turned out to be comparably active as homogeneous Grubbs II catalyst after immobilization on an acidic ion exchange resin which greatly facilitated workup.     

Green synthesis of 3,4-dihydropyrimidinones using nano Fe3O4@meglumine sulfonic acid as a new efficient solid acid catalyst under microwave irradiation

Design, synthesis and characterization of nano Fe₃O₄@meglumine sulfonic acid as a new solid acid catalyst for the simple and green one pot multicomponent synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones was studied. New solid acid catalyst was prepared through a clean and simple protocol and characterized using FTIR, VSM, TGA, SEM, elemental analysis (CHN) and XRD techniques. Heterogenization of homogeneous catalyst as a green approach is a useful method for enhancing the efficiency of catalyst. Presented study was a new method for attachment of homogeneous highly soluble catalyst (meglumine sulfate) to the magnetite nanoparticle surfaces for preparing a heterogeneous and effective catalyst. Obtained heterogeneous and reusable solid acid catalyst has high performance in the synthesis of Biginelli compounds. The reaction was performed under microwave irradiation as a rapid and green condition. Easy work up as well as excellent yield (90–98%) of products in short reaction times (40–200 s) and reusable catalyst are the main advantages of presented procedure. Reaction products were characterized in details using physical and chemical techniques such as melting point, ¹H NMR, ¹³C NMR and FTIR.     

Effect of catalyst aging on catalyst activity and stereospecificity for MgCl2/ethyl benzoate or dioctyl phthalate/TiCl4-triethylaluminium for propene polymerization

The aging of the MgCl₂/dioctyl phthalate (DOP) or ethyl benzoate (EB)/TiCl₄ catalyst was studied. Because of the strong complexation of DOP with the catalyst, only a small fraction of DOP was extracted by cocatalyst triethylaluminium (TEA) during aging, resulting in converting some highly isospecific sites into aspecific ones. No change of the overall number of sites was detected. EB, on the other hand, could be readily removed by TEA, resulting in a large increase in aspecific sites. Clustering of those sites facilitated catalyst deactivation.     

准均相的铂钯合金纳米催化剂用于芳香族化合物脱卤反应

用一锅法合成的负载于聚酰胺酸盐上的铂钯纳米催化剂,可以通过调节溶液的p H值实现催化剂与反应体系的有效分离和循环利用.准均相的铂钯催化剂应用于水相中卤代芳香族化合物的氢化脱卤反应,转化率达到99%以上,并且在重复使用5次后仍然保持很高的活性.铂钯双金属催化剂拥有比单一金属铂或者钯更高的催化活性,这主要是由于铂钯合金在催化反应时具有协同效应.利用X射线衍射仪(XRD),透射电子显微镜(TEM)等方法对催化剂进行了表征.数据表明铂钯纳米粒子负载于聚酰胺酸上以后可以在水溶液中稳定存在并且处于均匀的分布状态,纳米粒子尺寸约为4 nm.