Facile synthesis of ultrafine cobalt oxides embedded into N-doped carbon with superior activity in hydrogenation of 4-nitrophenol.

Design and synthesis of low-cost catalysts with high activity and stability for hydrogenation reactions is an important research area of applied catalysis. In this work, we present a kind of ultrafine cobalt oxides encapsulated by N-doped carbon (donated as CoOx/CN) as efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) process. The CoOx/CN was fabricated through a pyrolysis strategy using an N-containing metal-organic framework (Co-MOF) as precursor followed by a fine thermal-treatment. With an optimized pyrolysis temperature of 500 °C, the CoOx species present as ultrafine particles highly dispersed in the obtained catalyst (CoOx/CN-500). CoOx/CN-500 exhibits excellent activity and stability in hydrogenation of 4-NP at ambient conditions. The activity is much higher than that of not only bulk cobalt oxides, but also carbon supported CoOx catalysts. It could be used for more than 8 times without obvious fading in activity. In addition, the concrete role of Co-MOF precursor and pyrolysis condition in the catalyst design was investigated in detail. The interaction between organic ligands and Co ions and the confinement of the crystalline structure of Co-MOF could restrain the aggregation of Co ions during pyrolysis and lead to high dispersion of ultrafine CoOx species. Meanwhile, the N-containing ligands could be transformed into doped N species (pyridinic and pyrrolic N), endowing the CoOx species with high electron density and promoting the formation of active sites for the hydrogenation reaction.