Three-Dimensional Nitrogen-Doped Reduced Graphene Oxide-Carbon Nanotubes Architecture Supporting Ultrafine Palladium Nanoparticles for Highly Efficient Methanol Electrooxidation

A three-dimensional (3D) nitrogen-doped reduced graphene oxide (rGO)-carbon nanotubes (CNTs) architecture supporting ultrafine Pd nanoparticles is prepared and used as a highly efficient electrocatalyst. Graphene oxide (GO) is first used as a surfactant to disperse pristine CNTs for electrochemical preparation of 3D rGO@CNTs, and subsequently one-step electrodeposition of the stable colloidal GO-CNTs solution containing Na2PdCl4 affords rGO@CNTs-supported Pd nanoparticles. Further thermal treatment of the Pd/rGO@CNTs hybrid with ammonia achieves not only in situ nitrogen-doping of the rGO@CNTs support but also extraordinary size decrease of the Pd nanoparticles to below 2.0nm. The resulting catalyst is characterized by scanning and transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Catalyst performance for the methanol oxidation reaction is tested through cyclic voltammetry and chronoamperometry techniques, which shows exceedingly high mass activity and superior durability.