Platinum (Pt)-based electrocatalysts supported by reduced graphene oxide (RGO) were synthesized using two different methods, namely: (i) a conventional two-step polyol process using RGO as the substrate, and (ii) a modified polyol process implicating the simultaneous reduction of a Pt nanoparticle precursor and graphene oxide (GO). The structure, morphology, and electrochemical performances of the obtained Pt/RGO catalysts were studied and compared with a reference Pt/carbon black Vulcan XC-72 (C) sample. It was shown that the Pt/RGO obtained by the optimized simultaneous reduction process had higher Pt utilization and electrochemically active surface area (EASA) values, and a better performance stability. The use of this catalyst at the cathode of a proton exchange membrane fuel cell (PEMFC) led to an increase in its maximum power density of up to 17%, and significantly enhanced its performance especially at high current densities. It is possible to conclude that the optimized synthesis procedure allows for a more uniform distribution of the Pt nanoparticles and ensures better binding of the particles to the surface of the support. The advantages of Pt/RGO synthesized in this way over conventional Pt/C are the high electrical conductivity and specific surface area provided by RGO, as well as a reduction in the percolation limit of the components of the electrocatalytic layer due to the high aspect ratio of RGO.
In this paper, we for the first time demonstrate efficient nitrogen doping of graphene oxide (GO) with nitrogen concentration of up to almost 5 at.% and desired type of the nitrogen species via modified Hummers’ method. Using x-ray photoelectron spectroscopy (XPS), x-ray absorption spectroscopy (XAS) and Fourier transform infrared spectroscopy (FTIR) techniques, we have found out graphitic nitrogen to be the dominant type of the implemented nitrogen species. At the same time, the subsequent GO thermal reduction to graphene appears to result in a transformation of the graphitic nitrogen into pyridines and pyrroles. The mechanisms of the observed GO nitrogen doping and conversion of the nitrogen species are proposed, providing an opportunity to control the type and concentration of the implemented nitrogen within the developed approach. A two-time increase of the graphenes’ conductivity is observed due to the performed nitrogen doping. Further comprehensive electrical studies combined with the transmission electron microscopy (TEM) and density functional theory (DFT) modeling have allowed us to estimate the conductivity mechanism and the impact of the implemented nitrogen. As a net result, a simple method to synthesize GO and graphene layers doped with specific nitrogen species is developed, which leads to new perspective applications for graphene, i.e. supercapacitors, catalysis, and sensors.
A detailed study of the structure, morphology and electrochemical properties of Pt/C and Pt/x-SnO2/C catalysts synthesized using a polyol method has been provided. A series of catalysts supported on the SnO2-modified carbon was synthesized and studied by various methods including transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electrochemical methods, and fuel cell testing. The SnO2 content varies from 5 to 40 wt %. The TEM images, XRD and XPS analysis suggested the Pt-SnO2 hetero-clusters formation. The SnO2 content of ca. 10% ensures an optimal catalytic layer structure and morphology providing uniform distribution of Pt-SnO2 clusters over the carbon support surface. Pt/10wt %-SnO2/C catalyst demonstrates increased activity and durability toward the oxygen reduction reaction (ORR) in course of accelerated stress testing due to the high stability of SnO2 and its interaction with Pt. The polymer electrolyte membrane fuel cell current–voltage performance of the Pt/10wt %-SnO2/C is comparable with those of Pt/C, however, higher durability is expected.
Pt/C and Pt/SnOx/C catalysts were synthesized using the polyol method. Their structure, morphology and chemical composition were studied using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer, transition electron microscope and X-ray photoelectron spectroscope. Electrochemical measurements were based on the results of rotating disk electrode (RDE) experiments applied to ethanol electrooxidation. The quick evaluation of catalyst activity, electrochemical behavior, and an average number of transferred electrons were made using the RDE technique. The usage of SnOx (through the carbon support modification) in a binary system together with Pt causes a significant increase of the catalyst activity in ethanol oxidation reaction and the utilization of ethanol.