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考察了不同配体对原位合成的固载Ru基催化剂上CO2加氢合成HCOOH反应活性的影响,对于以单齿三苯基类ZPh3分子为配体的催化剂,活性大小顺序为:PPh3>AsPh3>NPh3.以PPh3为配体时,其相应的原位合成催化剂上HCOOH的TOF值为656h-1.其次,双齿膦配体的使用能带来比单齿膦配体更高的活性.以dppe[1,2-双(二苯基膦基)乙烷]为配体时,其相应的原位合成催化剂上HCOOH的TOF值为1190h-1.量子化学的理论计算结果表明,具有适中的σ给予性和π接受性,较小的空间位阻,较好的电子离域作用的PPh3配体性能优于其它单齿三苯基类配体.而具有较好的电子离域作用,并且有螯合作用的双齿膦配体性能优于单齿膦配体.
The effects of different ligands on the activity of CO2-hydrogenation of HCOOH on solid-supported Ru-based catalysts were investigated. For the catalysts with monodentate ZPh3 ligands, the order of activity was PPh3> AsPh3 > NPh3. When PPh3 is used as a ligand, the TOF value of HCOOH on the corresponding in-situ synthesized catalyst is 656h-1. Second, the use of bidentate phosphine ligands leads to higher activity than monodentate phosphine ligands. When dppe [1,2-bis (diphenylphosphino) ethane] was used as a ligand, the TOF value of HCOOH on the corresponding in-situ synthesized catalyst was 1190h-1. The theoretical calculations of quantum chemistry showed that moderate- Σ-acceptability and π-acceptability, less steric hindrance, better performance of electron-delocalization of PPh3 ligand than other monodentate triphenyl ligands.However, it has good electron delocalization, And chelating bidentate phosphine ligands perform better than monodentate phosphine ligands.