摘要
Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9%to aromatic haloamines can be achieved at the conversion of 100%.The results of H_2-TPD and FT-IR experiments show that Ni^-H~+ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation.When Raney Ni was treated by dicyandiamide,Ni^-H~+ species interacted with N atom from the dicyandiamide.This interaction was stable even at reaction temperature,which reduced the possibility to form the intermediate state of Ar-Cl...H~+Ni^-.And then C-Cl bond could not be polarized and activated.The hvdrodechlorination process was suppressed effectively.
Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9%to aromatic haloamines can be achieved at the conversion of 100%.The results of H_2-TPD and FT-IR experiments show that Ni^-H~+ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation.When Raney Ni was treated by dicyandiamide,Ni^-H~+ species interacted with N atom from the dicyandiamide.This interaction was stable even at reaction temperature,which reduced the possibility to form the intermediate state of Ar-Cl...H~+Ni^-.And then C-Cl bond could not be polarized and activated.The hvdrodechlorination process was suppressed effectively.
基金
the National Basic Research Program of China(973 Program)(No 2011CB710800)
the National Natural Science Foundation of China(No20976164)