【作者】 牛明铭；

【导师】 王艳华；

【作者基本信息】 大连理工大学 ， 有机化学， 2013， 博士

【摘要】 以聚乙二醇(PEG)为稳定剂,通过RuCl3·3H2O、RhCl3·3H2O、Na2PdCl4·xH2O的氢气还原法分别制得PEG稳定的Ru、Rh、Pd纳米催化剂。该催化剂与甲苯、正庚烷组成温控PEG两相催化体系具有“高温混溶,室温分相”的特性。即室温时,体系为两相,含有纳米催化剂的PEG相位于下层,上层为有机溶剂相；当升温至体系的混溶温度后,体系由两相变为均相；反应结束后,降至室温,体系又重新变为两相,通过简单分相即可将催化剂与产物分离并实现催化剂的循环使用。本文探索将上述含Ru、Rh、Pd纳米催化剂的温控PEG两相催化体系用于α,β-不饱和醛、酮、炔烃和喹啉的选择性加氢反应以及烯烃的氢氨甲基化反应中,催化剂均显示了较高的催化活性、选择性和良好的循环使用效果。具体研究结果如下：将PEG4000稳定的Pd纳米催化剂用于α,β-不饱和醛、酮的选择性加氢反应中。在优化的反应条件下：t=7h,T=120℃,PH2=4MPa,肉桂醛/Pd=1000(摩尔比值),肉桂醛转化率为99%,产物氢化肉桂醛的选择性为98%。催化剂可循环使用8次,催化活性基本保持不变,转化数TON值为8,642。首次将Ru纳米催化剂用于炔烃的选择性加氢反应。以PEG2000稳定的Ru纳米催化剂催化丙炔酸甲酯的选择性加氢反应为例,在优化的反应条件下：t=10h,T=100℃, PH2=2.0MPa,丙炔酸甲酯/Ru=1000(摩尔比值),丙炔酸甲酯的转化率和产物丙烯酸甲酯的选择性分别为92%和97%。催化剂可循环使用10次,催化活性基本保持不变,转化数TON值为9,717。将PEG4000稳定的Rh纳米催化剂用于喹啉的选择性加氢反应中。在优化的反应条件下：t=3h,T=100℃,PH2=3MPa,喹啉/Rh=1000(摩尔比值),喹啉的转化率为97%,产物1,2,3,4-四氢喹啉的选择性高于99%。催化剂可循环使用10次,催化活性基本保持不变,转化数TON值为10,592。将PEG4000稳定的铑纳米催化剂用于烯烃的氢氨甲基化反应中。以1-辛烯与二正丙胺的氢氨甲基化反应为例,在优化的反应条件下:t=4h,T=120℃,P=6MPa(CO/H2=1：1),1-辛烯/Rh=1000(摩尔比值),1-辛烯的转化率和产物胺的选择性分别为99%和90%。催化剂循环使用20次,催化活性基本保持不变,转化数TON值达19,080,是目前文献中报道的最高值。更多还原

【Abstract】 Soluble Ru, Rh and Pd nanoparticles were prepared by hydrogen reduction of the corresponding RuCl3·3H2O, RhCl3·3H2O or Na2PdCl4·xH2O in the presence of poly(ethylene glycol)(PEG). The thermoregulated PEG biphasic system composed of PEG-stabilized Ru, Rh or Pd nanoparticles and a mixture of toluene and n-heptane possesses the thermoregulated phase-transition property, that is, at room temperature, the lower PEG phase containing Ru, Rh or Pd nanoparticles was immiscible with the upper organic phase consisting of toluene and n-heptane. Interestingly, when the temperature was elevated gradually to the miscibility temperature of the system, the biphasic system merged into a single phase. Finally, by decreasing the temperature to room temperature again, the system recovered to the biphasic form. The product and the catalyst were collected easily from the organic and PEG phase, respectively. The recovered catalyst can be reused without further purification or activation. This methodology opens up a new avenue for recovery and recycling of soluble transition-metal nanoparticle catalysts, especially for noble transition-metal nanoparticle catalysts. In this dissertation, PEG-stabilized Ru, Rh or Pd nanoparticles were employed as catalysts for the selective hydrogenation of α,β-unsaturated aldehydes or ketones, alkynes and quinoline. Moreover, PEG-stabilized Rh nanoparticles were also investigated in the hydro-aminomethylation of olefins. The results were as follows:PEG4000-stabilized Pd nanoparticles were used as catalysts for the selective hydro-genation of α,β-unsaturated aldehydes or ketones. Under the optimized reaction conditions:t=7h, T=120℃, PH2=4MPa, cinnamaldehyde/Pd=1000(molar ratio), the conversion of cinnamaldehyde and the selectivity of hydrocinnamaldehyde were99%and98%, respectively. The catalyst could be reused for eight times without evident loss in activity or selectivity. The value of turnover number (TON) was8,642.Ru nanoparticles were used as catalysts for the selective hydrogenation of alkynes for the first time. For the PEG2000-stabilized Ru nanoparticle catalyzed selective hydrogenation of methyl propiolate, under the optimized reaction conditions:t=10h, T=100℃, PH2=2.0MPa, methyl propiolate/Ru=1000(molar ratio), the conversion of methyl propiolate and the selectivity of methyl acrylate were92%and97%, respectively. The catalyst could be reused for ten times without evident loss in activity or selectivity. The value of TON reached9,717.PEG4000-stabilized Rh nanoparticles were used as catalysts for quinoline. Under the optimized reaction conditions:t=3h, T=100℃, PH2=3MPa, quinoline/Rh=1000(molar ratio), the conversion of quinoline and the selectivity of1,2,3,4-tetrahydroquinoline were97%and99%, respectively. The catalyst could be reused for ten times without evident loss in activity or selectivity. The value of TON was10,592.Furthermore, PEG4000-stabilized Rh nanoparticles were employed as catalysts for the hydroaminomethylation of olefins. Under the optimized reaction conditions:t=4h, T=120℃, P=6MPa (CO/H2=1:1),1-octene/Rh=1000(molar ratio), the conversion of1-octene and the selectivity of amines were99%and90%, respectively. The catalyst could be reused for twenty times without evident loss in activity or selectivity. The value of TON was up to19,080, the highest TON reported so far in literatures.更多还原