稀土镧改性磷钨杂多酸盐催化油酸与甲醇酯化反应合成生物柴油活性研究

以H ₃PW ₁₂O ₄₀和La(NO ₃) ₃为原料,通过离子交换法制备一种稀土镧改性磷钨杂多酸盐催化剂.通过扫描电镜、红外光谱和X射线粉末衍射等表征方法,对合成的催化剂的物理及化学性能进行分析,进而通过以油酸和甲醇为反应物的酯化反应,对其催化活性进行研究.结果表明:稀土镧已经导入磷钨杂多酸的骨架结构,并与杂原子P形成配位键,有效提高磷钨杂多酸的比表面积和孔径;合成的催化剂具有完整的Keggin型结构;当反应温度为62 ℃,油酸与甲醇摩尔比为1∶6,反应时间为4.5 h,催化剂用量为反应物质量的2.5 %,油酸的转化率可达88.0 %.      

Lewis酸型固体酸催化剂Ce-Ag-PW的制备、表征及催化酯化反应合成生物柴油性能研究

通过超声浸渍法,经Ce3+和Ag+协同改性磷钨杂多酸（HPW）制备了一种以Lewis酸性活性位为主的固体酸催化剂Ce-Ag-PW。采用X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、扫描电镜（SEM）、透射电镜（TEM）、热重（TG）、NH₃程序升温脱附（NH₃-TPD）、吡啶吸附红外光谱（Py-IR）和X射线光电子能谱（XPS）等表征手段对其物理化学性能进行了表征分析。并以Ce-Ag-PW为经甲醇和油酸酯化反应来合成生物柴油的催化剂,对其的催化活性和稳定性进行了研究。结果表明,Ce-Ag-PW具有高催化活性和稳定性,以其为催化剂,当甲醇与油酸的物质的量比为14: 1,催化剂用量为反应物总质量的2%,反应温度为65 ℃,反应6 h后,油酸的转化率即高达91%。固体酸催化剂在经过4次循环使用后,油酸的转化率仍可达到80.5%。Ce-Ag-PW的高催化活性和稳定性可归因于Ag+可置换HPW中的质子,以及Ce3+的强吸电子作用,使其由Br?nsted酸型催化剂转化为以Lewis酸型为主的催化剂。由于Br?nsted酸位易与酯化反应过程中生成的水发生水合反应而失活,因而Lewis酸位的形成有助于减少催化剂的失活现象发生。因此,当通过油酸与甲醇酯化反应合成生物柴油时,Ce-Ag-PW是一种具有高催化活性和稳定性的以Lewis酸性活性位为主的固体酸催化剂。      

钼钨硅杂多酸稀土盐的合成与表征

用复分解法合成出通式为ＬｎＨＳｉＭｏ１０Ｗ２Ｏ４０·ｘＨ２Ｏ（Ｌｎ＝Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｙｂ）十种钼钨硅杂多酸稀土盐，利用ＩＲ、ＵＶ、ＸＲＤ进行了表征，借助ＴＧ－ＤＴＡ对配合物的热解性质进行了研究，得到了配合物热稳定存在的温度范围为４００～４５０℃。     

金钨杂多酸—罗丹明B缔合显色反应的研究

金钨杂多酸－罗丹明Ｂ缔合显色反应的研究李祟宁，李祖碧，杜超（云南大学成人教育学院，昆明，６５００９１）徐其亨（云南大学化学系，昆明，６５００９１）三苯甲烷染料－卤金酸或氯化亚锡络阴离子离子缔合物［１，２］，灵敏度高，但稳定性差（特别是温度影响大），应...     

Keggin结构钼钨硅杂多酸及其稀土衍生物的氧化还原性质研究

利用循环伏安和极谱研究了Ｋｅｇｇｉｎ结构钼钨硅杂多酸Ｈ４ＳｉＭｏ１２－ｎＷｎＯ４０（记为ＳｉＭｏ１２－ｎＷｎ，ｎ＝２，４，６，８，１０）及其稀土衍生物Ｋ１０Ｈ３〔Ｌｎ（ＳｉＭｏ６Ｗ５Ｏ３９）２〕（记为Ｌｎ（ＳｉＭｏ６Ｗ５）２，Ｌｎ＝Ｌａ３＋，Ｃｅ３＋，Ｐｒ３＋，Ｎｄ３＋，Ｓｍ３＋，Ｅｕ３＋，Ｇｄ３＋，Ｄｙ３＋，Ｙｂ３＋）在水溶液中的氧化还原性质，讨论了取代原子和酸度对杂多阴离子氧化还原性质的影响，探讨了极谱半波电位与ｐＨ的关系，并根据静电模型对杂多配合物的氧化还原规律性给予了合理的说明。     

磷钨钒杂多酸催化α-甲基丙烯酸甲酯酯交换反应的研究

利用差示扫描量热法(DSC)测定Dawson型磷钨钒杂多酸对甲基丙烯酸甲酯的阻聚效果,选择其中阻聚性能最佳的杂多酸.以α-甲基丙烯酸甲酯和正丁醇为原料,在不加任何阻聚剂的条件下,以阻聚性能最佳的杂多酸为催化剂,通过酯交换法合成α-甲基丙烯酸丁酯单体,采用正交实验探讨了影响反应的主要因素,确定了合成α-甲基丙烯酸丁酯的最佳工艺条件:n(α-甲基丙烯酸甲酯)∶n(正丁醇)=1.2∶1,磷钨钒杂多酸催化剂用量为反应液总量的0.6%,反应时间为8 h,反应温度为125℃.在此条件下,α-甲基丙烯酸丁酯的收率可达90%以上.用红外光谱和核磁共振谱对产物进行了结构表征,证实其结构与用常规酯化法合成的产物并无明显差异.     

二氧化硅负载磷钨杂多酸催化合成环己酮乙二醇缩酮

采用浸渍制备了二氧化硅负载磷钨杂多酸催化剂。以环己酮和乙二醇为原料合成环己酮乙二醇缩酮,探讨了二氧化硅负载磷钨杂多酸催化剂对缩酮反应的催化活性,较系统地研究了原料量比、催化剂用量和反应时间诸因素对产品收率的影响。实验表明,二氧化硅负载磷钨杂多酸是合成环己酮乙二醇缩酮的良好催化剂,在n（环己酮）∶n（乙二醇）=1∶1.4,催化剂用量为反应物料总质量的0.4%,带水剂环己烷的用量为8ml和反应时间1.0h的优化条件下,环己酮乙二醇缩酮的收率可达87.3%。     

钽酸的合成、表征及催化酯化反应性能

采用KOH熔融法合成了钽酸.利用X射线衍射仪,傅里叶变换红外光谱仪,热重分析仪和紫外-可见-近红外光谱仪对合成的钽酸进行表征.结果表明:钽酸中存在1.8个水,且在制备过程中吸附了硫酸根,经850℃焙烧3 h,钽酸大部分转化为Ta2O5.以钽酸为催化剂,研究其催化正丁醇与冰乙酸反应生成乙酸正丁酯中各种因素对酯化率的影响.实验证明钽酸是合成乙酸正丁酯的良好催化剂.反应条件为:HAc0.167 mol,n(醇):n(酸)=2:1,催化剂用量为HAc质量的7.5%,带水剂环己烷5 ml,回流反应5 h,酯化率达88.8%.     

铈钨改性HMS的制备及其催化合成乳酸戊酯

制备了铈钨改性分子筛Ce-W/HMS,并用于催化乳酸和正戊醇的酯化反应合成了乳酸戊酯。采用IR分析对催化剂进行了表征。考察了催化剂的焙烧时间、催化剂用量、醇酸物质的量比、反应时间、催化剂的重复使用性等因素对酯化率的影响。结果表明,nSi∶nW∶nCe=30∶1∶1,600℃焙烧2 h,0.2 mol乳酸,催化剂0.5g,醇酸物质的量比1.2,反应时间1.5 h,酯化率可达90.85%。该催化剂重复使用5次的酯化率仍可达87.28%。     

镧系元素的双(九钨二钒)杂多酸钾的合成与表征

报道了镧系元素钨钒杂多配合物的合成方法。元素分析和热重分析确定其通式为：Ｋ１０Ｈ７〔Ｌｎ（Ｖ２Ｗ９Ｏ３７）２〕·ｘＨ２Ｏ（Ｌｎ＝Ｓｍ３＋、Ｅｕ３＋、Ｇｄ３＋）。利用红外（ＩＲ）、紫外（ＵＶ）和Ｘ射线衍射谱对其进行了表征。配合物的热解性质研究表明，其分解温度范围为４００～４５０℃。     

钨钼混配型杂多酸盐催化剂上酯化反应条件的优化研究

以Na2WO4·2H2O和 Na2MoO4·2H2O为原料,通过硝酸酸化-乙醚萃取法制备了一种钨钼混配型杂多酸盐催化剂（Na4SiMoW12O40·xH2O）.应用X射线荧光光谱对合成的催化剂的元素组成进行了分析;通过红外光谱对其的官能团结构进行了分析;借助热重分析对其的热稳定性进行了研究.并以正丁醇和乙酸为反应物,研究了所制备的钨钼混配型杂多酸盐在催化酯化反应时的活性和稳定性.通过正交试验[L9（3）4]对影响乙酸正丁酯收率的关键影响参数进行了优化,包括催化剂与反应物的质量比、反应时间和温度、以及正丁醇与乙酸的摩尔比.结果表明：当反应时间为120 min,反应温度为90℃,催化剂用量为0.4 g,醇酸摩尔比为2∶1,酯化效果最好,达到93.24 wt%.     

Schiff碱单核与双核配合物的抗菌及催化活性研究

合成了双核[Cu(HL)(CH3OH)](1)和单核[Cu(HI)2](2)(H2L=水杨醛缩乙醇胺)2个Schiff碱铜配合物.采用元素分析和x射线单晶衍射对配合物的组成和结构进行了表征.采用琼脂扩散法测定了配体和配合物的抑菌活性,同时研究了不同条件下配合物对H2O2分解的催化性能.实验表明:目标化合物对革兰氏阳性菌具有较好的抑制作用,并且配合物1的抑菌活性优于配体和配合物2;在碱性条件下,0.008 g配合物1作为催化剂,对15 mL15%过氧化氢溶液的催化分解效果最佳,同时配合物1的催化活性明显高于配合物2和相应金属盐的催化活性.     

Controllable preparation of CeO2 nanostructure materials and their catalytic activity

Well-crystalline CeO2 nanostructures with the morphology of nanorods and nanocubes were synthesized by a template-free hydro-thermal method. X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) nitrogen adsorp-tion-desorption measurements were employed to characterize the synthesized materials. The reducibility and catalytic activity of nanostruc-tured CeO2 were examined by hydrogen temperature-programmed reduction (H2-TPR) and CO oxidation. The results showed that CeO2 nanorods could be converted into CeO2 nanocubes with the increasing of the reaction time and the hydrothermal temperature, CeO2 nanorods became longer gradually with the increasing of the concentrations of NaOH. H2-TPR characterization demonstrated that the intense low-temperature reduction peak in the CeO2 nanorods indicated the amount of hydrogen consumed is larger than CeO2 nanocubes. Meantime the CeO2 nanorods enhanced catalytic activity for CO oxidation, the total conversion temperature was 340 oC. The reasons were that CeO2 nanorods have much smaller crystalline sizes and higher surface areas than CeO2 nanocubes.     

Effect of preparation method on the catalytic activity of Au/CeO2 for VOCs oxidation

The Au/CeO2 catalysts were synthesized by co-precipitation (CP), deposition-precipitation (DP) and metallic colloids deposition (MCD) method, and tested for oxidation of volatile organic compounds (VOCs). It was revealed that the Au/CeO2 catalyst prepared by DP method was the most efficient catalyst towards the total oxidation of toluene. The Au/CeO2 catalysts had obviously high catalytic activity, and the best results was obtained on 3 wt.% Au/CeO2 catalyst prepared by DP method. These catalysts were chara...     

Effects of arachidonic, linoleic, linolenic and oleic acid on experimental arrhythmias in cats, rabbits and guinea-pigs

Antiarrhythmic effects of the Prostaglandin (PG) precursors arachidonic and Linoleic acid were demonstrated on three models of experimental arrhythmias, whereas the fatty acids linolenic and oleic acid proved to be ineffective in these models. In ouabain-induced arrhythmias infusions of arachidonic acid (1, 0 mg/kg/min) caused a strong antiarrhythmic effect in 80 percent of the animals. On the same model linoleic acid showed a maximum effct in 40 percent of the animals. BaCl2-induced arrhythmias were abolished by arachidonic and linoleic acid in 60 percent and 66 percent of the rabbits, respectively. Pretreatment by indomethacin reduced the antiarrhythmic effects of linoleic acid from 40 percent to 9 percent on ouabain-induced arrhythmias in cats. The results suggest a participation of PG synthesis in the antiarrhythmic effect of PG precursors.     

Studies on the activity, properties and isoenzymes of acid phosphatase in the erythrocytes of swine, horse, dog, cat, duck and chicken

Acid phosphatase of erythrocytes of several species was investigated, with three isozymes having been recorded from swine (three types), three (two types) from horse, four (one type) from dog, two (two types) from cat, two (three types) from duck, and two (one type) from fowl. The Michaelis constant of the enzyme varied between 3.5 and 5 X 10(-4) M for the species involved. The species, however, differed slightly for the optimum pH of the enzyme. The average enzymatic activities were (5.68 +/- 0.42 for dog, 4.46 +/- 1.0 for horse, 3.8 +/- 0.24 for swine, 3.72 for cat, 2.5 +/- 0.62 for duck, and 1.9 +/- 0.8 for fowl. All values are units per gram haemoglobin. Even relatively low concentrations (0.2 or 1 mM) of copper, mercury, and cadmium ions were found to be strong inhibitors of the acid erythrocyte phosphatase.