Intermittent microwave synthesis of nanostructured Pt/TiN–graphene with high catalytic activity for methanol oxidation

A one-step and fast microwave technique was developed to synthesize graphene-supported TiN nanoparticles (TiN–G) directly from graphene and dihydroxybis (ammonium lactato) titanium (IV). During the synthesis graphene served as a reductant and template to reduce the Ti-precursor into TiN and then uniformly disperse TiN nanoparticles on it. Pt/TiN–G catalyst was also successfully prepared with the portion of Pt nanoparticles was anchored at the interface of TiN and graphene. Electrochemical measurements showed that the Pt/TiN–G catalyst exhibited improved catalytic activity for methanol oxidation and enhanced CO tolerance than those of Pt/G catalyst, attributed to the formation of –OH groups on the surface of TiN. And the –OH attached TiN assisted the conversion of CO into CO₂.     

Mesoporous tungsten carbide-supported platinum as carbon monoxide-tolerant electrocatalyst for methanol oxidation

This paper reports a CO-tolerant electrocatalyst, mesoporous tungsten carbide-supported platinum (Pt/m-WC), for methanol oxidation. The support m-WC was synthesized by evaporation-induced triconstituent co-assembly method in which phenol formaldehyde polymer resin was used as the carbon precursor, tungsten hexachloride as the tungsten precursor and an amphiphilic triblock copolymers (P123) as the template. Nano-sized platinum particles were loaded on the m-WC to prepare Pt/m-WC. The structure and morphology of the prepared electrocatalyst were characterized by transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) and X-ray diffraction (XRD), and its activity toward methanol oxidation and its tolerance for CO were determined by cyclic voltammetry (CV) and chronopotentiometry (CP). It is found that the m-WC carburized at 900 °C(m-WC-900) has a larger specific surface area (182 m² g⁻¹) and a appropriate crystal structure compared to the m-WC carburized at 800 °C or 1000 °C, and thus is better as the support of platinum. The prepared Pt/m-WC-900 exhibits higher activity toward methanol oxidation and better tolerance for CO than Pt/Vulcan XC-72. The onset potential of CO electro-oxidation on Pt/m-WC is 0.449 V, which is more negative than that on Pt/Vulcan XC-72 (0.628 V).     

Preliminary studies of the electrochemical performance of Pt/X@MoO3/C (X = Mo2C,MoO2, Mo) catalysts for the anode of a DMFC: Influence of the Pt loading and Mo-phase

The present study is focused on the influence of Pt loading on the reactivity of catalysts prepared supporting the metal on novel core–shell molybdenum substrates. The electrocatalytic activity and stability of nine Pt/X@MoO3/C catalysts (where X denotes the nature of Mo-phases in the core of the core–shell Mo-particle: Mo₂C, MoO₂ and/or Mo⁰) with three Pt loading (5, 20 and 30 wt% Pt) were tested for carbon monoxide and methanol electro–oxidation reactions.     

Pt/C catalyst impregnated with tungsten-oxide – Hydrogen oxidation reaction vs. CO tolerance

Hydrogen Oxidation Reaction (HOR) is anode reaction in Proton exchange membrane fuel cells (PEMFCs) and it has very fast kinetics. However, the purity of fuel (H₂) is very important and can slow down HOR kinetics, affecting the overall PEMFC performance. The performance of commercial Pt/C catalyst impregnated with WO_x, as a catalyst for HOR, was investigated using a set of electrochemical methods (cyclic voltammetry, linear scan voltammetry and rotating disk electrode voltammetry). In order to deepen the understanding how WO_x species can contribute CO tolerance of Pt/C, a particular attention was paid to CO poisoning. In the absence of CO, HOR is under diffusion limitations and HOR kinetics is not affected by WO_x species. Appreciable HOR current on the electrodes pre-saturated with CO_ads at potentials above 0.3 V vs. RHE, which is not observed for pure Pt/C, was discussed in details. HOR liming diffusion currents for higher concentrations of W are reached at high anodic potentials. The obtained results were explained by donation of OH_ads by WO_x phase for CO_ads removal in the mid potential region and reduced reactivity of Pt surface sites in the vicinity of the Pt|WO_x interface. The obtained results can provide guidelines for development of novel CO tolerant PEMFC anode catalysts.     

Electrocatalytic activity of Pt nanoparticles electrodeposited on amorphous carbon-coated silicon nanocones

This study pulse-electrodeposits Pt nanoparticles on amorphous carbon-coated silicon nanocones (ACNCs) and explores them as the electrocatalyst for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) for direct methanol fuel cell applications. The work prepares silicon nanocones on the Si wafer using porous anodic aluminum oxide as the template and then deposits the amorphous carbon layer on the nanocones by microwave plasma chemical vapor deposition. According to Raman scattering and X-ray photoelectron spectroscopies (XPS), the surface of the ACNC support is composed of a nanocrystalline graphitic structure, and rich in oxygen-containing adspecies. The Pt nanoparticles pulse-electrodeposited on the highly ordered ACNC support disperses well with a large electrocatalytic surface area. The Pt/ACNC electrode exhibits excellent electrocatalytic activity and stability toward both MOR and ORR. This study suggests the abundant oxygen-containing surface species and the nanometer size of the Pt catalyst as the two major factors enhancing electrocatalytic performance of Pt/ACNC electrode. The XPS study suggests the occurrence of charge transfer from π-sites of the graphitic structure to the Pt nanoparticle, thereby improving the electrochemical stability of the electrode.     

Effect of process variables on Pt/CeO2 catalyst behaviour for the PROX reaction

A Pt/CeO₂ catalyst has been evaluated for CO oxidation, both in the absence of H₂ and in H₂-rich feedstreams. The catalyst shows high activity and selectivity at temperatures as low as 80 °C, what makes it a viable catalyst for the selective depletion of CO in the temperature range at which PEMFC operate. The effect of: oxygen excess during operation (λ)$(\lambda )$, the presence of either CO₂ (5%), H₂O (5%) or both in the feedstream, and the spatial time, on catalyst activity and selectivity has been evaluated.     

Ordered silicon nanocones as a highly efficient platinum catalyst support for direct methanol fuel cells

Platinum nanoparticles were electrodeposited on ordered silicon nanocones (SNCs) and used as the catalyst for methanol electro-oxidation in direct methanol fuel cells (DMFCs). Because of uniform dispersion of Pt nanoparticles and the high surface area, the Pt-SNC electrode exhibited superior electrocatalytic properties toward the methanol electro-oxidation, with the onset potential of 0.08 V (vs. SCE). According to chronoamperometric analysis and CO stripping cyclic voltammetric (CV) study, the Pt/SNC electrode had a stable electro-oxidation activity with a very good CO tolerance. The Si surface oxide surrounding the Pt nanoparticles on the SNCs was suggested to play a key role in improving the CO tolerance via the bifunctional mechanism.     

Enhanced electrocatalytic activity of high Pt-loadings on surface functionalized graphene nanosheets for methanol oxidation

Here we report a simple one-pot microwave-polyol reduced method to anchor platinum nanoparticles on graphene with the aid of poly (diallyldimethylammonium chloride) (PDDA), forming a Pt/PDDA–G hybrid (Pt/PDDA–G). High Pt metal loadings, up to 85 wt.% with a mean size of 1.4 nm, were densely in situ decorated on PDDA-modified graphene surfaces. The electrochemical tests showed that the activity and stability of Pt supported on PDDA–graphene hybrid substrates for methanol oxidation were better than that of Pt supported on graphene sheets, also better than the widely used Pt/carbon black electrocatalysts with the same Pt content on the electrode. This improved activity indicates that PDDA plays a crucial role in the highly dispersion and stabilization of Pt nanoparticles on graphene and PDDA–G are able to an alternative support for Pt immobilization in direct methanol fuel cells.     

Methanol oxidation reaction on Ti/RuO2(x)Pt(1−x) electrodes prepared by the polymeric precursor method

In this work, ruthenium oxide films containing platinum nanoparticles were prepared using the polymeric precursor method on Ti substrates with several molar ratios. This paper aims at presenting the characterization of the Pt content effect in the methanol electrochemical oxidation reaction. The films were physically characterized using X-ray diffraction and both Pt and RuO₂ (rutile) phases were observed. The mean crystallite sizes were 6 nm for Pt and 25 nm for RuO₂. The X-ray photoelectronic results indicated that on the electrodes surfaces, depending on the substrate, there was RuO₂, Ru metal and Pt metal. Besides, it was not observed the formation of PtRu alloys. The atomic force microscopy images of the films showed highly rough surfaces. A decrease in the roughness mean square values is observed as the Pt content increases. These last results are similar to electroactive surface area values calculated by redox-couple (K₄FeCN₆/K₃FeCN₆). There was an increase in the globular size observed on the electrode surface and lower particle dispersion as the Pt content is increased from 12.5 to 75 mol%. Regarding the eletrode electrocatalytical behavior for methanol oxidation, it was observed that the onset oxidation overpotential is displaced towards more negative values as Pt content is decreased. Besides, an increase has been shown in the current density for methanol oxidation of 600% using a Ti/RuO₂-Pt (87.5:12.5) electrode compared to polycrystalline Pt.     

CO electrooxidation study on Pt and Pt-Ru in H3PO4 using MEA with PBI-H3PO4 membrane

CO electrooxidation on Pt and Pt-Ru in H₃PO₄ was studied in the temperature range 120-180 °C using CO-N₂-H₂O gas mixtures of controlled composition. On Pt and Pt-Ru the voltammetry curves exhibited Tafel behavior in a wide potential range with a slope of 80-100 mV per decade. Replacement of Pt with Pt-Ru on the anode resulted mainly in a shift of CO electrooxidation voltammetry curves by approx. −0.3 V. Reaction order in respect to water vapor pressure was found close to unity with both electrocatalysts. Reaction order in respect to CO partial pressure was found negative, close to zero. Values of apparent activation energy of CO electrooxidation on these electrocatalysts were nearly equal, E_a app = 110 ± 15 kJ mol⁻¹. The results were interpreted within the framework of Langmuir-Hinshelwood mechanism. An equation, which describes the observed features of CO electrooxidation on Pt and Pt-Ru, was suggested. Comparing results of the present study with results of earlier studies of CO tolerance of Pt and Pt-Ru electrocatalysts, it was concluded that CO electrooxidation can hardly play a significant role in CO tolerance of PEM FC with PBI-PA membranes.     

Impact of dehydrogenation on the methanol oxidation reaction occurring on carbon nanotubes supported Pt catalyst with low Pt loading

The electro-catalytic methanol oxidation reaction (MOR) has received considerable research attention due to its importance in the development of direct methanol fuel cells. In this study, the dehydrogenation step in MOR was investigated using low levels of platinum (Pt) which supported on carbon nanotubes as a catalyst. The concentration of H⁺ had a significant effect on the MOR activity of Pt catalysts supported by carbon nanotubes (Pt/CNTs), indicating that the dehydrogenation process was a critical step in MOR for Pt/CNTs with low Pt loading. Furthermore, the effects of Pt particle size and the distance between the Pt particles were investigated. We suggested a hypothesis: for the Pt catalyst with large particle size, only a few particles were needed for dehydrogenation to proceed; for the Pt catalyst with small particle size, many Pt particles were needed to form a network for the dehydrogenation reaction, but when the Pt particles were close enough, only a few Pt particles were needed. Our study provided insight into the electro-catalytic activity of Pt/CNTs from a mechanistic perspective.     

CO tolerance and durability study of PtMe(Me = Ir or Pd) electrocatalysts for H2-PEMFC application

In the present work, carbon supported PtMe (Me = Ir or Pd) electrocatalysts, with different atomic ratios (Pt/Me (20 wt%) = 3:1, 1:1, 1:3), are thoroughly investigated towards CO tolerance and durability, as anode and cathode for H₂-PEMFCs (hydrogen fed proton exchange membrane fuel cells) application. The electrocatalysts are prepared via a pulse-microwave assisted polyol synthesis method and their durability and electrocatalytic activity in presence and absence of CO are evaluated using the techniques of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA) and rotating disk electrode (RDE). For the investigation of CO tolerance a protocol is set that could be used by other research groups, since various procedures are reported in literature. It is found that Pd/C shows higher CO tolerance than Pt/C, while the PtPd₃/C exhibits the highest CO tolerance ability, even after being exposed for 9 h at 400 ppm CO. Despite the fact that Pt₃Ir/C shows higher CO tolerance ability than Pt/C, it cannot resist at such high CO concentrations for more than 6 h. Finally, it is found that PtIr/C and PtPd/C exhibit very good durability even after 5000 accelerated durability test (ADT) cycles, while Pt₃Pd/C and PtPd/C present the highest mass activities (339.4 and 410 mA/mg_Pt respectively at 0.9 V), which are 4 and 5 times higher than the one observed over commercial Pt/C (82.75 mA/mg_Pt).     

Preparation of Pt/NiO-C electrocatalyst and heat-treatment effect on its electrocatalytic performance for methanol oxidation

Pt catalyst supported on Vulcan XC-72R containing 5 wt% NiO (Pt/NiO–C) showed larger electrochemical active surface area and higher electrochemical activity for methanol oxidation than Pt catalyst supported on Vulcan XC-72R using polyol method without NiO addition. Prepared Pt/NiO–C electrocatalyst was heat-treated at four temperatures (200, 400, 600, and 800 °C) in flowing N₂. X-ray diffraction and temperature-programmed desorption results indicated that NiO was reduced to Ni in inert N₂ during heat-treatments at temperatures above or equal to 400 °C, while oxygen from NiO reacted with carbon support due to the catalytic effect of Pt. The reduced Ni formed an alloy with Pt, which, according to the X-ray photoelectron spectroscopy data, resulted in a shift to a lower binding energy of Pt 4f electrons. The Pt/NiO–C electrocatalyst heat-treated at 400 °C showed the best activity in methanol oxidation due to the change in Pt electronic structure by Ni and the minimal aggregation of Pt particles.