Poly(vinylpyrrolidone)-Modified Graphite Carbon Nanofibers as Promising Supports for PtRu Catalysts in Direct Methanol Fuel Cells

Carbon nanomaterials, including herringbone graphite carbon nanofibers (GNFH), multiwalled carbon nanotubes (MWCNT), and carbon black, were surface-modified by a new poly(vinylpyrrolidone) (PVP) grafting process as well as by the conventional acid-oxidation (AO) process, and characterized by FTIR, TGA, Raman, HRTEM, XRD, and XPS measurements. Pt nanoparticles of 1.8 nm were evenly deposited on all PVP-grafted carbon nanomaterials. The effects of the two surface modification processes on the dispersion, average Pt nanoparticle sizes, the electrocatalytic performance, and electrical conductivities of Pt−carbon nanocomposites in direct methanol oxidation were systematically studied and compared. It was found that the PVP-grafted carbon nanomaterials have much less loss in the electric conductivity and thus better electrocatalytic performance, 17−463% higher, than their corresponding acid oxidation-treated nanocomposites. The electrocatalytic performance of the Pt−carbon nanocomposites decreases in the following order: Pt−PVP−GNFH > Pt−PVP−MWCNTarc > Pt−AO-MWCNTarc > Pt−PVP−MWCNTCVD > Pt−AO-MWCNTCVD > Pt−XC-72R > Pt−AO-GNFH, with the Pt−PVP−GNFH nanocomposite having ∼270% higher performance than that of the Pt−Vulcan XC-72R nanocomposite. In addition, PtRu−PVP−GNFH shows even better (50% higher) electrocatalytic activity than the Pt−PVP−GNFH nanocomposite at a 0.6 V applied voltage.