Hierarchical Graphitic Carbon-Encapsulating Cobalt Nanoparticles for Catalytic Hydrogenation of 2,4-Dinitrophenol

Cobalt hierarchical graphitic carbon nanoparticles (Co@HGC) (1), (2), and (3) were prepared by simple pyrolysis of a cobalt phenanthroline complex in the presence of anthracene at different temperatures and heating times, under a nitrogen atmosphere. The samples were used for the catalytic hydrogenation of 2,4-dinitrophenol. Samples (1) and (3) were prepared by heating at 600 °C and 800 °C respectively, while (2) was prepared by heating at 600 °C with an additional intermediate stage at 300 °C. This work revealed that graphitization was catalyzed by cobalt nanoparticles and occurred readily at temperatures of 600 °C and above. The nanocatalysts were characterized by Scanning Electron Microscopy SEM, energy dispersive X-ray analysis EDX, Raman, Xrd, and XPS. The analysis revealed the presence of cobalt and cobalt oxide species as well as graphitized carbon, while TEM analysis indicated that the nanocatalyst contains mainly cobalt nanoparticles of 3–20 nm in size embedded in a lighter graphitic web. Some bamboo-like multiwall carbon nanotubes and graphitic onion-like nanostructures were observed in (3). The structures and chemical properties of the three catalysts were correlated with their catalytic activities. The apparent rate constants kapp (min−1) of the 2,4-dinitrophenol reductions were 0.34 for (2), 0.17 for (3), 0.04 for (1), 0.005 (no catalyst). Among the three studied catalysts, the highest rate constant was obtained for (2), while the highest conversion yield was achieved by (3). Our data show that an increase in agglomeration of the cobalt species reduces the catalytic activity, while an increase in pyrolysis temperature improves the conversion yield. The nanocatalyst enhances hydrogen generation in the presence of sodium borohydride and reduces 2,4-dinitrophenol to p-diamino phenol. The best nanocatalyst (3) was prepared at 800 °C. It consisted of uniformly distributed cobalt nanoparticles sheltered by hierarchical graphitic carbon. The nanocatalyst is easily separated and recycled from the reaction system and proved to be degradation resistant, to have robust stability, and high activity towards the reduction reaction of nitrophenols.