纳米氧化铝负载双硫腙分离富集-原子吸收法测定地质样品中的金、铂、钯的研究

金、铂、钯在地质样品中的含量甚微,国内外常采用ICP-AES,ICP-MS和ETAAS直接测定。FAAS法由于仪器便宜、操作方便,也广泛应用于预富集后的痕量贵金属的分析。目前,在测定贵金属的分析方法中,常采用固相萃取法富集分离样品,主要的固相萃取剂有:无机吸附剂,交联树脂[1],螯合树脂[     

Synthesis and Mesomorphic Behavior of 3‐Alkyl‐2,5‐ bis[p‐(hexa‐2,4‐dienoyloxy)phenyl]‐Thiophene Derivatives

3‐Alkyl‐2,5‐bis[p‐(hexa‐2,4‐dienoyloxy)phenyl]‐thiophene derivatives were synthesized by using Kumada coupling and Suzuki coupling reactions as key steps. The thermotropic liquid crystalline behavior of these compounds was investigated by optical polarized microscopy, monotropic nematic mesophases were observed in such compounds.     

原子层沉积构筑Pd/TiO2限域催化剂及其在1,4-丁炔二醇加氢的应用

利用ALD制备了TiO₂限域的Pd催化剂, 研究了限域空间内Pd纳米颗粒与TiO₂的界面作用对1,4-丁炔二醇(BYD)加氢性能的影响. 相比于管外负载型催化剂, 限域催化剂在催化1,4-丁炔二醇选择性加氢反应中体现出非常高的催化活性和1,4-丁烯二醇的选择性. HR-TEM、 EDX-Mapping、 XRD、 XPS和H₂-TPR表征说明, 限域体系中Pd-TiO₂的界面相互作用强于传统TiO₂表面负载型Pd催化剂, 这种强界面作用不仅能够提高BYD的加氢活性, 也可抑制半加氢产物1,4-丁烯二醇的异构化和深度加氢, 提高1,4-丁烯二醇的选择性, 而且限域结构也可阻止管内壁Pd纳米颗粒的脱落, 提高催化剂的稳定性.     

氟喹诺酮作为钯催化Heck反应有效配体的研究

研究了氟喹诺酮作为钯催化Heck反应的有效配体. 碘苯、溴苯和其它芳基卤衍生物与丙烯酸丁酯、苯乙烯等取代乙烯类化合物在钯和氟喹诺酮的催化下发生Heck反应. 讨论了配体、催化剂用量、碱和溶剂对Heck反应产率的影响. 该反应的最优化条件是: 钯源为Pd(OAc)2 (0.1 mol%), 诺氟沙星作为配体(0.2 mol%), K2CO3作为碱, DMA作为溶剂, 取代碘苯及溴苯和它们的衍生物与丙烯酸丁酯、苯乙烯等乙烯基化合物的反应均可以得到高收率的目标偶联产物.     

A sulfur-tolerant Pd/CeO2 catalyst for methanol synthesis from syngas

The catalytic activity of cefia-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditions. The bifunctional nature of this catalyst opens a route for the conversion of sulfur-contaminated gas streams such as the integrated gasification combined cycle syngas or biogas into liquid fuels if desulfurization by conventional means is not practical.     

CO在Pd／ZrO2—Al2O3催化剂上表面反应性能的研究

用流动反应法和ＴＰＳＲＭＳ等技术研究了ＣＯ在Ｐｄ／γＡｌ２Ｏ３和含有ＺｒＯ２的催化剂上的吸脱附行为、表面反应及催化氧化活性，同时用ＸＲＤ技术测定了催化剂的物相结构。结果表明，在Ｐｄ／γＡｌ２Ｏ３催化剂中用浸渍法添加ＺｒＯ２或掺杂超细ＺｒＯ２后，催化剂的氧化活性均有明显提高；ＣＯＴＰＳＲ的实验结果表明，ＣＯ在氧化态Ｐｄ催化剂上程序升温脱附过程中主要与表面氧发生氧化反应，而在还原态Ｐｄ催化剂上发生歧化反应，并发现ＣＯ２的脱附量及脱附峰温次序与对ＣＯ的氧化活性有一致的对应关系。     

Electrode kinetics and thermodynamic study of complexes of palladium(II) at D.M.E.

Polarographic study of Pd(II) reveals that it reduces quasireversibly at d.m.e. in 0.2M-pyridine+0.1N-HCl medium. Kinetic parameters of Pd(II) in various concentrations of -resorcyclic acid were calculated usingGellings method and thus the effect of concentration of -resorcyclic acid on the kinetics of the reduction of Pd(II) has been explained.DeFord/Hume graphical extrapolation method and the mathematical method ofMihailov have been employed for the evaluation of overall formation constants of the complexes formed with -resorcyclic acid. The logarithmic values of overall formation constants ₁, ₂ and ₃ obtained by the two methods are 7.47, 8.60, 9.66 (DeFord andHume Method) and 7.44, 8.64, 9.66 (Mihailov Method) at 298 K. Thermodynamic parameters of these complexes are reported.

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Elektrodenkinetik und thermodynamische Untersuchungen an Pd(II)-Komplexen mittels polarographie

Zusammenfassung Pd(II) zeigt eine quasireversible Reduktion in 0,2M-Pyridin/0,1N-HCl. Kinetische Parameter wurden mittels der Methode vonGelling ermittelt und damit der Effekt verschiedener -Resorcylsäurekonzentrationen erklärt. Bildungskonstanten der entsperechenden Komplexe wurden nachDeFord/Hume und nachMihailov ermittelt. Die logarithmischen Werte der Gesamtbildungskonstanten ₁, ₂ und ₃ bei 298 K betragen nach derDe Ford/Hume-Methode 7,47, 8,60 und 9,66, nach derMihailov-Methode 7,44. 8,64 und 9,66. Die thermodynamischen Parameter der Komplexbildung werden angegeben.

     

Palladium-catalyzed cross-coupling reaction of alkynylzincs with benzylic electrophiles

The reaction of alkynylzinc bromides with benzyl bromides or chlorides in the presence of a catalytic amount of Pd(DPEphos)Cl₂ in THF at 23 °C cleanly produces the corresponding benzylated alkynes in 73-97% yields. With 10⁻³ mol % of Pd(DPEphos)Cl₂, the maximum turnover number of 7.1 × 10⁴ has been observed for the formation of PhCCCH₂Ph.