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Hybrid supports composed of chemically-reduced graphene-oxide-aligned with tungsten oxide nanowires are considered here as active carriers for dispersed platinum with an ultimate goal of producing improved catalysts for electroreduction of oxygen in acid medium. Here WO3 nanostructures are expected to be attached mainly to the edges of graphene thus making the hybrid structure not only highly porous but also capable of preventing graphene stacking and creating numerous sites for the deposition of Pt nanoparticles. Comparison has been made to the analogous systems utilizing neither reduced graphene oxide nor tungsten oxide component. By over-coating the reduced-graphene-oxide support with WO3 nanorods, the electrocatalytic activity of the system toward the reduction of oxygen in acid medium has been enhanced even at the low Pt loading of 30 microg cm-2. The RRDE data are consistent with decreased formation of hydrogen peroxide in the presence of WO3. Among important issues are such features of the oxide as porosity, large population of hydroxyl groups, high Broensted acidity, as well as fast electron transfers coupled to unimpeded proton displacements. The conclusions are supported with mechanistic and kinetic studies involving double-potential-step chronocoulometry as an alternative diagnostic tool to rotating ring-disk voltammetry., Comment: arXiv admin note: text overlap with arXiv:1805.03152

We report here on a novel and facile techniques for the synthesis nanocomposite based on stable bimetallic catalyst containing iridium and gold nanoparticles electrodeposited on chemically reduced graphene oxide (rGO) sheet admixed with platinum nanoparticles as an efficient electrocatalyst to facilitate the oxygen reduction reaction (ORR) in acidic medium. Raman spectroscopy, infrared spectroscopy (IR), scanning electron microscope (SEM), transmission electron microscope (TEM) methods were employed to characterize the rGO, Au-NPS-rGO, Ir-NPS-rGO, Au-Ir-rGO nanocomposites formed on the electrode surface. Here we present a comparative study into the relative effects of each hybrid nanocomposites: Au-NPS-rGO, Ir-NPS-rGO, Au-Ir-rGO nanocomposites on the performance of platinum nanoparticles towards the oxygen reduction reaction (ORR) in acidic media. For the purposes of comparing the supports, a simple platinum black catalyst is used and the performance isevaluated via direct measurement of peroxide by rotating ring-disk electrode (RRDE) to determine the number of electrons (n) transferred in the ORR. It was found that platinum nanoparticles dispersed within Au-Ir-rGO support follows a quasi 4-electron mechanism (3.99-4 electrons involved) due to that the ORR takes place mainly on the active Pt particles, and produced hydrogen peroxide is reduced at Au-Ir-rGO support.

Silver-iron carbon nitride has been obtained by pyrolysis (under inert atmosphere) of silver hexacyanoferrate(II), precipitated on graphene nanoplatelets, and examined as electrocatalyst for oxygen reduction reaction in alkaline media in comparison to silver nanoparticles and iron carbon nitride (prepared separately in a similar manner on graphene nanoplatelets). The catalytic materials have been studied in 0.1 M potassium hydroxide electrolyte using such electrochemical diagnostic techniques as cyclic voltammetry and rotating ring-disk electrode voltammetry. Upon application of graphene nanoplateletssupported mixed silver-iron carbon nitride catalyst, the reduction of oxygen proceeds at more positive potentials and the amounts of hydrogen peroxide (generated during reduction of oxygen at potentials more positive than 0.3 V) are lower relative to silver nanoparticles and iron carbon nitride (supported on graphene nanoplatelets) examined separately. Promoting effect is ascribed to high activity of silver toward the reduction/decomposition of H2O2 in basic medium. Additionally, it has been observed that the systems based on carbon nitrides show considerable stability due to strong fixation of metal complexes to CN shells.

Here we develop a class off face centred cubic structure of metallic silver nanocrystals, to enable high ORR activity process. Silver nanoparticles deposited within different carbon supports: carboxylated-graphene, SiO2-doted reduced- graphene-oxide (Gr/SiO2) and reduced-graphene-oxide (Gr) were prepared. The reduction of silver ions and the formation of silver nanoparticles deposited within graphene-type supports have been assessed by UV-Vis spectroscopy and was confirmed by XRD studies. The major advantage of the proposed chemical synthetic method is the integration of the superb properties of both silver nanoparticles and graphene supports in a single-step synthesis with a 100% usage of the silver precursor (AgNO3). The choice of the carbon support strongly affected catalytic activity of the resulting Ag nanoparticles towards oxygen electroreduction in alkaline medium. We show that SiO2-doted reduced- graphene-oxide supported silver nanoparticles display significantly enhanced catalytic activity towards the oxygen reduction reaction (ORR) in alkaline solutions compared to the silver nanoparticles immobilized within carboxylated-graphene support and chemically reduced graphene oxide (Gr). Moreover under RRDE conditions the hybrid material based on SiO2-doted reduced- graphene-oxide supported silver nanoparticles displays the most impressive electrocatalytic performance toward ORR and shows the highest number of exchanged electrons (n) ranging from 3.96 to 3.998 when compared to the silver nanoparticles immobilized within carboxylated-graphene support (3.90-3.994) and reduced-graphene-oxide (Gr) supported silver nanoparticles (3.88-3.991).

Hybrid systems composed of the reduced graphene oxide-supported platinum and multiwall carbon nanotubes-supported iridium (both noble metals utilized at low loadings on the level of 15 and < 5 microg cm-2, respectively) have been considered as catalytic materials for the reduction of oxygen in acid media (0.5 mol dm-3 H2SO4). The electrocatalytic activity toward reduction of oxygen and formation of hydrogen peroxide intermediate have been tested using rotating ring-disk electrode voltammetric experiments. The efficiency of the proposed catalytic systems has also been addressed by performing galvanodynamic measurements with gas diffusion electrode half-cell at 80 {\deg}C. The role of carbon nanotubes is to improve charge distribution at the electrocatalytic interface and facilitate the transport of oxygen and electrolyte in the catalytic systems by lowering the extent of reduced graphene oxide restacking during solvent evaporation. The diagnostic electrochemical experiments reveal that at iridium-containing systems not only higher disk currents, but also much smaller ring currents have been produced (compared to reduced graphene oxide-supported platinum and its composite with bare carbon nanotubes), clearly implying formation of lower amounts of the undesirable hydrogen peroxide intermediate. The enhancement effect coming from the addition of traces of iridium (supported onto carbon nanotubes) to Pt, utilized at low loading, may originate from the high ability of Ir to induce decomposition of the undesirable hydrogen peroxide intermediate. There is a competition between activation (due to the presence of small amounts of Ir) and dilution (by carbon nanotubes) of Pt active centers in hybrid systems, therefore special attention is paid to the adjustment of their composition.

Chemically-reduced graphene-oxide-supported gold nanoparticles are considered here as catalytic materials for the reduction of oxygen in alkaline medium. Gold nanoparticles are prepared by the chemical reduction method, in which the NaBH4-prereduced Keggin-type phosphomolybdate heteropolyblue acts as the reducing agent for the precursor (HAuCl4). Polyoxmetallate (PMo12O403-) capping ligands stabilize gold nanoparticle deposits, facilitate their dispersion and attachment to carbon supports. Indeed, it is apparent from the independent diagnostic voltammetric experiments (in 0.5 mol dm-3 H2SO4) that heteropolymolybdates form readily stable adsorbates on nanostructures of both gold and carbon (reduced graphene oxide and Vulcan). It is reasonable to expect that the polyoxometallate-assisted nucleation of gold has occurred in the proximity of oxygenated defects existing on carbon substrates. Under conditions of electrochemical diagnostic experiments (performed in 0.1 mol dm-3 KOH): (i) the phosphomolybdate adsorbates are removed from the interface as they undergo dissolution in alkaline medium; and (ii) the Au nanoparticles (Au loading, 30 {\mu}g cm-2) remain well-dispersed on the carbon as evident from transmission electron microscopy. High electrocatalytic activity of the reduced-graphene oxide-supported Au nanoparticles toward reduction of oxygen in alkaline medium is demonstrated using cyclic and rotating ring-disk voltammetric experiments. Among important issues are possible activating interactions between gold and the support, as well as presence of structural defects existing on poorly organized graphitic structure of reduced graphene oxide (as evident from Raman spectroscopy).

Graphene is, in principle, a promising material for consideration as component (support, active site) of electrocatalytic materials, particularly with respect to reduction of oxygen, an electrode reaction of importance to low-temperature fuel cell technology. Different concepts of utilization, including nanostructuring, doping, admixing, preconditioning, modification or functionalization of various graphene-based systems for catalytic electroreduction of oxygen are elucidated, as well as important strategies to enhance the systems' overall activity and stability are discussed.

Novel member of polymetalloporphines, namely manganese polymetalloporphine of type I (pMnP-I) obtained by ion exchange from magnesium polyporphine of type I (pMgP-I) is reported for the first time and compared to its cobalt analogue (pCoP-I). Both polymer films have been obtained via two-step procedure: demetalation of the pMgP-I electrode film via its exposure to trifluoroacetic acid solution, resulting in formation of the metal-free polyporphine of type I (pH2P-I) followed by electrochemically induced incorporation of Co or Mn ions from the acetonitrile solution of cobalt and manganese perchlorates. A further oxidative transformation of pCoP-I, pMnP-I polymer films has led to the corresponding polyporphines of type II, pCoP-II and pMnP-II, possessing such unique features as condensed polymer structure with a very high density of active sites and high electronic conductivity within a very broad potential range including the one corresponding to the neutral (uncharged) state of the polymer matrix. Both polymers of type II also exhibit interesting electrocatalytic activity toward oxygen electroreduction in aqueous neutral (pH 6.7) and alkaline (pH 13) media which was evaluated under cyclic voltammetric and steady-state conditions. The results demonstrate that the efficiency (regardless of the electrolyte) of both polymetalloporphines is comparable to bare platinum electrode. The effect of annealing of polymer-modified electrodes on their catalytic properties has also been considered.

Application of graphene-type materials in electrocatalysis is a topic of growing scientific and technological interest. A tremendous amount of research has been carried out in the field of oxygen electroreduction, particularly with respect to potential applications in the fuel cell research also with use of graphene-type catalytic components. This work addresses fundamental aspects and potential applications of graphene structures in the oxygen reduction electrocatalysis. Special attention will be paid to creation of catalytically active sites by using non-metallic heteroatoms as dopants, formation of hierarchical nanostructured electrocatalysts, their long-term stability, and application as supports for dispersed metals (activating interactions).

We report on the development of two new Pt-free electrocatalysts (ECs) for the oxygen reduction reaction (ORR) based on graphene nanoplatelets (GNPs). We designed the ECs with a core-shell morphology, where a GNP core support is covered by a carbon nitride (CN) shell. The proposed ECs present ORR active sites that are not associated to nanoparticles of metal/alloy/oxide, but are instead based on Fe and Sn sub-nanometric clusters bound in coordination nests formed by carbon and nitrogen ligands of the CN shell. The performance and reaction mechanism of the ECs in the ORR are evaluated in an alkaline medium by cyclic voltammetry with the thin-film rotating ring-disk approach and confirmed by measurements on gas-diffusion electrodes. The proposed GNP-supported ECs present an ORR overpotential of only ca. 70 mV higher with respect to a conventional Pt/C reference EC including a XC-72R carbon black support. These results make the reported ECs very promising for application in anion-exchange membrane fuel cells. Moreover, our methodology provides an example of a general synthesis protocol for the development of new Pt-free ECs for the ORR having ample room for further performance improvement beyond the state of the art.

This work reports the synthesis, the physicochemical characterization and the electrochemical studies of new electrocatalysts (ECs) for the oxygen reduction reaction (ORR) that: (i) are based on a hierarchical graphene-based support; and (ii) do not comprise platinum. The active sites of the ECs consist of Fe and Sn species stabilized in 'coordination nests' of a carbon nitride (CN) matrix. The latter exhibits a rough, microporous morphology and acts as a 'shell' covering a graphene 'core'. This paper: (i) discusses the role played by Fe as the 'active metal' in this family of ECs; and (ii) examines in detail how the physicochemical properties and, correspondingly, the electrochemical performance are affected by a suitable activation procedure A meant to boost the ORR kinetics. The results lead to an improved fundamental understanding on the features of the active sites, including the impact of both A and the pH of the environment in their performance and ORR mechanism. These insights clarify the most desirable features to be included in high-performing ECs belonging to this family, paving the way to the synthesis of next-generation, efficient ECs for the ORR that do not comprise platinum.