Size-Dependent Halogenated Nitrobenzene Hydrogenation Selectivity of Pd Nanoparticles

The selective hydrogenation of halogenated nitrobenzene (HNB) has been a great important chemical reaction in the fine chemical productions. In this study, the effect of metal particle size on the selective hydrogenation of HNB over Pd/C catalysts has been extensively investigated through the combination of theoretical (density functional theory calculations, DFT) and experimental methods. DFT calculations showed that the reaction barriers for dechlorination strongly depend on the type of reaction sites (terrace or edge), while the hydrogenation reaction barriers are nearly the same on different sites, which indicates that Pd nanoparticle size significantly affects the catalyst selectivity. Moreover, Pd nanoparticles with different sizes (from 2.1 to 30 nm) supported on activated carbon were synthesized using the methods developed by our group. In a 500 mL reactor, the selectivity is over 99.90% when the Pd nanoparticles are bigger than 25 nm. Finally, the industrial applications of the proposed catalyst were evaluated in several pilot factories. This study provides useful information on controlling the selectivity of other similar reactions catalyzed by noble-metal nanocatalysts