Effects of specific nitrogen functionality and oxidative functionalization of the surfaces of nitrogen-doped carbon nanotubes (NCNTs) on the interaction between Pt nanoparticles (NPs) and NCNTs have been systematically investigated. Their catalytic consequences were studied using aerobic oxidation of glycerol and electro-oxidation of CO as probing reactions. By transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and X-ray diffraction (XRD), it was revealed that nitrogen dopant obviously enhanced the dispersion of Pt NPs. Strong interaction between Pt and NCNTs was observed. Graphitic nitrogen preferentially interacted with Pt NPs, evidenced by strong electron transfer from graphitic nitrogen as electron donor to metallic Pt NPs. The oxygen-containing groups introduced by H2O2 oxidation of NCNTs may reduce the donor-acceptor interaction due to the electronegativity of oxygen. By changing the nitrogen amount of NCNTs and introducing oxygen groups, the electron enrichment of Pt NPs can be tuned. Superior catalytic activity was achieved over Pt/NCNTs in the oxidation of glycerol and electro-oxidation of CO, compared with conventional carbon nanotubes as support. Moreover, for both aerobic oxidation of glycerol and electro-oxidation of CO, it was observed that the intrinsic activity depended strongly on the electron enrichment of Pt NPs, ascribed to Pt4f(7/2)(0) binding energy from XPS, suggesting a promising approach to improving catalytic activity by maximizing the interaction between Pt NPs and graphitic nitrogen sites. (C) 2015 Elsevier Inc. All rights reserved.