Cold Plasma Preparation of Pd/Graphene Catalyst for Reduction of p-Nitrophenol.

Supported metal nanoparticles with small size and high dispersion can improve the performance of heterogeneous catalysts. To prepare graphene-supported Pd catalysts, graphene and PdCl2 were used as support and Pd precursors, respectively. Pd/G-P and Pd/G-H catalysts were prepared by cold plasma and conventional thermal reduction, respectively, for the catalytic reduction of p-nitrophenol (4-NP). The reaction followed quasi-first-order kinetics, and the apparent rate constant of Pd/G-P and Pd/G-H was 0.0111 and 0.0042 s-1, respectively. The graphene support was exfoliated by thermal reduction and cold plasma, which benefits the 4-NP adsorption. Pd/G-P presented a higher performance because cold plasma promoted the migration of Pd species to the support outer surface. The Pd/C atomic ratio for Pd/G-P and Pd/G-H was 0.014 and 0.010, respectively. In addition, the Pd nanoparticles in Pd/G-P were smaller than those in Pd/G-H, which was beneficial for the catalytic reduction. The Pd/G-P sample presented abundant oxygen-containing functional groups, which anchored the metal nanoparticles and enhanced the metal-support interaction. This was further confirmed by the shift in the binding energy to a high value for Pd3d in Pd/G-P. The cold plasma method operated under atmospheric pressure is effective for the preparation of Pd/G catalysts with enhanced catalytic activity for 4-NP reduction.