Well-designed electronic configurations and structural properties of electrocatalyst alter the activity, stability, and mass transport for enhanced catalytic reactions. We introduce a nanofibrous oxide-carbon composite by an in situ method of carbon nanofiber (CNF) growth by highly dispersed Ni nanoparticles that are exsoluted from a NiTiO3 surface. The nanofibrous feature has a 3D web structure with improved mass-transfer properties at the electrode. In addition, the design of the CNF/TiO2 support allows for complex properties for excellent stability and activity from the TiO2 oxide support and high electric conductivity through the connected CNF, respectively. Developed CNF/TiO2-Pt nanofibrous catalyst displays exemplary oxygen-reduction reaction (ORR) activity with significant improvement of the electrochemical surface area. Moreover, exceptional resistance to carbon corrosion and Pt dissolution is proven by durability-test protocols based on the Department of Energy. These results are well-reflected to the single-cell tests with even-better performance at the kinetic zone compared to the commercial Pt/C under different operation conditions. CNF/TiO2-Pt displays an enhanced active state due to the strong synergetic interactions, which decrease the Pt d-band vacancy by electron transfer from the oxide-carbon support. A distinct reaction mechanism is also proposed and eventually demonstrates a promising example of an ORR electrocatalyst design.
Keywords: PEMFC cathode catalyst; electrochemical stability; electronic configuration; nanofibrous structure; oxide−carbon composite support.