Palladium oxide (PdO) nanoparticles supported on B, Al and Ga modified mesoporous MCM-41 with different Si/M ratios (where, M = B, Al or Ga) varied from 100 to 5 was synthesized in one-pot. Developed materials were characterized by several techniques such as XRD, TEM, UV-Vis, XPS and TG-DTA. A highly ordered structure was revealed by XRD for all the support materials depending on Si/M ratio. TEM analysis evidenced the presence of spherical PdO particles. Interestingly, the particle sizes correlated well with Si/M ratio as well as the nature of M. Spectroscopic characterization of calcined materials suggested the presence of Pd2+, whereas XPS confirmed the existence of Pd2+ in PdO form. The catalytic activity of resultant materials was investigated by the chemoselective hydrogenation of chloronitrobenzene in supercritical carbon dioxide. All the materials exhibit excellent conversion of chloronitrobenzene and selectivity to chloroaniline within the reaction time of 50 min. at 35 degrees C. Substitution of Si by trivalent metal cation improved the catalytic performance of B and Ga containing catalysts. Among the three catalysts, superior catalytic activity was observed for Pd/B-MCM-41 with highest conversion (100%) and selectivity to chloroaniline (100%) and thus, followed the reactivity order of PdO/B > PdO/Ga > PdO/Al. Considering o-, m- and p-chloronitrobenzene, for all the materials conversion followed the order of p- > m- > o-, whereas selectivity to chloroaniline for all three isomers were strongly influenced by the trivalent metal ion in the support material. (C) 2014 Elsevier Inc. All rights reserved.