Liquid-Phase Hydrogenation of Halobenzenes in the Presence of Palladium-Containing Nanodiamonds

Abstract

The catalytic activity of palladium-containing nanodiamonds (Pd/ND) is studied in the model reaction of liquid-phase hydrodehalogenation of monohalobenzenes (chlorobenzene, bromobenzene, and iodobenzene) and ortho-, meta-, and para-isomers of dichlorobenzene under mild conditions (Т = 45°С, \({{P}_{{{{{\text{H}}}_{2}}}}}\) = 1 atm). The obtained results are compared with the catalytic behavior of the palladium-containing activated carbon (Pd/C) under identical conditions. It is found that catalyst Pd/ND is more active than Pd/C and is more stable against the poisonous effect of hydrogen halide forming during the reaction. Study of the effect of HCl and NaOH additives on the catalyst activity shows that, in the presence of HCl, poisoning of the catalyst occurs: the rate of reaction decreases; in the presence of NaOH, the catalyst activity grows; the rate of reaction increases as a result of hydrogen chloride neutralization by an alkali. For both catalysts the rate of reaction decreases in the sequence Cl > Br > I for monohalobenzenes and in the sequence para- > ortho- > meta-isomer in the case of dichlorobenzenes. The obtained dependences are explained using the quantum-chemical modeling of substrates of model reactions.