Selective gas phase hydrogenation of p-Chloronitrobenzene over Pd catalysts: Role of the support

The gas phase (1 atm, 453 K) hydrogenation of p-chloronitrobenzene (p-CNB) over a series of laboratory-synthesized and commercial Pd (1-10% wt) supported on activated carbon (AC) and non-reducible (SiO2 and Al2O3) and reducible (ZnO) oxides has been examined. Reaction over these catalysts generated the target p-chloroaniline (p-CAN) (via selective hydrogenation) and nitrobenzene (NB)/aniline (AN) as a result of a combined hydrodechlorination/hydrogenation. A range of Pd nanoparticles with mean sizes 2.4-12.6 nm (from HRTEM and H-2/CO chemisorption) were generated. Both the p-CNB transformation rate and H-2 chemisorption increased with decreasing Pd size. Residual Mo (from the stabilizer used in the synthesis of Pd colloids) suppressed activity, but this was circumvented by the use of poly(N-vinyl-2-pyrrolidone) (PVP). Pd/AC generated p-CAN and AN as principal products, Pd on SiO2 and Al2O3 exhibited hydrodechlorination character generating AN and NB, and Pd/ZnO promoted the sole formation of p-CAN at all levels of conversion. Reaction selectivity is linked to Pd electron density with the formation of Pd delta+ on AC and the occurrence of Pd delta+ on SiO2 and Al2O3. Reaction exclusivity to p-CAN over Pd/ZnO is attributed to the formation of PdZn alloy (demonstrated by XPS), which selectively activates the -NO2 group. This is the first report that demonstrates 100% selectivity for p-CNB -> p-CAN over supported Pd.