Synthesis and electro-catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes

Template synthesis of various nitrogen containing carbon nanotubes using different nitrogen containing polymers and the variation of nitrogen content in carbon nanotube (CNT) on the behaviour of supported Pt electrodes in the anodic oxidation of methanol in direct methanol fuel cells was investigated. Characterizations of the as-prepared catalysts are investigated by electron microscopy and electrochemical analysis. The catalyst with N-containing CNT as a support exhibits a higher catalytic activity than that carbon supported platinum electrode and CNT supported electrodes. The N-containing CNT supported electrodes with 10.5% nitrogen content show a higher catalytic activity compared to other N-CNT supported electrodes. This could be due to the existence of additional active sites on the surface of the N-containing CNT supported electrodes, which favours better dispersion of Pt particles. Also, the strong metal-support interaction plays a major role in enhancing the catalytic activity for methanol oxidation.     

Methanol oxidation activities of Pt nanoparticles supported on microporous carbon with and without a graphitic shell

Platinum nanoparticles were prepared as catalysts supported on microporous amorphous carbon with and without a graphitic carbon shell. The electro-oxidation of methanol in acidic solutions at room temperature was used as a probe reaction to explore the effect of the carbon structure on catalysis. CO anodic stripping voltammetry and cyclic voltammetry both recorded enhanced performance for the catalyst supported on the carbon with a graphitic shell. Some rationalizations of the possible roles of the graphitic shell are provided.     

Selective oxidation of methylamine over zirconia supported Pt-Ru,Pt and Ru catalysts

Pt–Ru, Pt and Ru catalysts supported on zirconia were prepared by impregnation method and were tested in se-lective oxidation of methylamine (MA) in aqueous media. Among three catalysts, Ru/ZrO2 was more active than Pt/ZrO2 while Pt–Ru/ZrO2 demonstrated the best catalytic activity due to the fact that Pt addition efficiently pro-moted the dispersion of active species in bimetallic catalyst. Therefore, the~100%TOC conversion and N2 selec-tivity were achieved over Pt–Ru/ZrO2, Pt/ZrO2 and Ru/ZrO2 catalysts at 190, 220 and 250 °C, respectively.     

Methanol oxidation at Pt/MoO x /MoSe2 thin film electrodes prepared with exfoliated MoSe2

This paper presents results on the dispersion of Pt on MoO _x /MoSe₂ electrodes, which were prepared by an intercalation–exfoliation technique. The Pt/MoO _x /MoSe₂ electrodes were tested for methanol oxidation by cyclic voltammetry. Thin films of MoSe₂ can be oxidized electrochemically to form a MoO _x layer. Compared with pure platinum, Pt/MoO _x /MoSe₂ electrodes gave lower oxidation potentials and higher current densities. We believe that methanol adsorption and subsequent dehydrogenation occur at the Pt atoms, while the OH_ads nucleation occurs at Mo sites. The presence of the adsorbed —OH groups on Mo sites may catalyze CO oxidation to CO₂. This surface reaction is necessary for the improved electrocatalytic behavior of Pt/MoO _x /MoSe₂ electrodes.     

Methanol partial oxidation on carbon-supported Pt and Pd catalysts

Different Pt and Pd catalysts supported on an activated carbon were prepared by using different metal precursors. Prepared catalysts were pretreated at 400 °C under different atmospheres to decompose the precursor compound and reduce the metal. After pretreatments, the supported catalysts were characterized by H₂ chemisorption, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy to know their metal dispersion, particle size, distribution and oxidation state. Afterwards, the catalysts were tested in methanol partial oxidation with two different O₂/CH₃OH molar ratios. Results obtained in this reaction were compared with those obtained for methanol decomposition in inert atmosphere. For Pt catalysts, there was an increase in methanol conversion and hydrogen production and a decrease in carbon monoxide production under oxidizing conditions. Both methanol conversion and partial oxidation reactions appear to be sensitive to Pt particle structure in the particle size range studied. Results obtained under oxidizing conditions differed between Pd and Pt catalysts. Finally, catalytic activity in methanol partial oxidation was more affected by Pt than Pd particle size in the size range studied.     

Formic acid oxidation on Pd-modified Pt(100) and Pt(111) electrodes: A DEMS study

Formic acid oxidation on palladium submonolayers on well-defined Pt(100) and Pt(111) electrodes has been studied using voltammetry and Differential Electrochemical Mass Spectrometry (DEMS). A combination of the two techniques allows a better understanding of the reaction taking place on the electrode surface. Thus, an exact correlation between the CO₂ mass signal and the current density in the voltammogram corresponding to the formic acid oxidation has been obtained. On palladium modified Pt(100) electrodes and in the potential region below 0.3 V, the currents in the positive scan are higher than those recorded in the negative scan. This diminution on the signal in the negative scan has been associated with CO₂ reduction to CO on the palladium adlayer. In addition, the CO₂ reduction reaction seems to take place on the border of the palladium islands. Finally, the adsorption of (bi)sulfate anions has an inhibiting behavior on the formic acid oxidation reaction.     

Electro-catalytic oxidation of CO on Pt catalyst supported on carbon nanotubes pretreated with oxidative acids

Characteristics of nanosized Pt electro-catalyst deposited on carbon nanotubes (CNTs) were studied with CO-stripping voltammogram and chronoamperometry measurements. The CNTs were pretreated by oxidation in HNO₃, mixed HNO₃ + H₂SO₄ and H₂SO₄ + K₂Cr₂O₇ solution, respectively, to enable surface modification. Well-homogenized Pt particles (average size: ≈3 nm) were loaded onto the pretreated CNT samples by a modified colloidal method. TEM, BET, FTIR and XRD techniques were used to characterize the physicochemical properties of the pretreated CNT samples. In the electro-oxidation of CO, all the Pt/CNT samples showed lower on-set as well as peak potentials than the conventional Pt/XC-72 electro-catalyst, indicating that the Pt/CNT samples were more resistant to CO poisoning and could be superior anode electro-catalyst for the proton exchange membrane fuel cells (PEMFCs). Moreover, we found that the pretreatment of CNTs in mixed HNO₃ + H₂SO₄ solution was very beneficial for the performance enhancement of Pt/CNT electro-catalyst; the catalyst obtained as such gave the lowest peak potential and the highest catalytic activity for the electro-oxidation of CO. Larger amount of oxygen-containing functional groups, higher percentage of mesopores, and higher graphitic crystallinity of the pretreated CNTs were considered crucial for the performance enhancement, e.g., by strengthening the interaction between Pt nanoparticles and the CNT support and enhancing the mass diffusion in the electro-chemical reaction.     

A kinetic and DRIFTS study of supported Pt catalysts for NO oxidation

NO oxidation was studied over Pt/CeO₂ and Pt/SiO₂ catalysts. Apparent activation energies (E _a) of 31.4 and 40.6 kJ/mole were determined for Pt/CeO₂ and Pt/SiO₂, respectively, while reaction orders for NO and O₂ were fractional and positive for both catalysts. Pre-treatment of the catalysts with SO₂ caused a decrease in the E _a values, while the reaction orders were only slightly changed. In situ DRIFTS measurements indicated that high concentrations of nitrate species were formed on the surface of Pt/CeO₂ during NO oxidation, while almost no surface species could be detected on Pt/SiO₂. The addition of SO₂ resulted in the formation of a highly stable sulfate at the expense of nitrate species and caused an irreversible loss of catalytic activity for Pt/CeO₂.     

Some aspects of limonene oxidation at Pt electrodes in aqueous and acetonitrile solutions

Limonene oxidation does not occur at reasonable rates in aqueous media, but it is found that in acidified acetonitrile solutions containing some water, steady-state currents can be maintained. Obtained data suggest that water addition to a double bond happens before electrochemical oxidation in the acetonitrile solution takes place.     

Methanol oxidation on carbon-supported Pt-Ru and TiO2 (Pt-Ru/TiO2/C) electrocatalyst prepared using polygonal barrel-sputtering method

Methanol oxidation performance of a carbon-supported Pt-Ru alloy catalyst used at the direct methanol fuel cell (DMFC) anode is improved by adding TiO₂. However, the methanol oxidation performance of the electrocatalyst described above must be enhanced further to realize practical application in DMFCs. In this study, we used our original surface-modifying technique termed the “polygonal barrel-sputtering method” to prepare a carbon-supported Pt-Ru and TiO₂ (Pt-Ru/TiO₂/C) electrocatalyst offering higher methanol oxidation performance. The obtained results show that the methanol oxidation performance of the prepared Pt-Ru/TiO₂/C is superior to that using wet process as the TiO₂ deposition method. Furthermore, for our sputtering method, the peak current of methanol oxidation on the Pt-Ru/TiO₂/C is enhanced by increasing the TiO₂ deposited amount up to 2.8 wt.%. These results suggest that a Pt-Ru/TiO₂ interface area is increased using the polygonal barrel-sputtering method, providing the high methanol oxidation performance of Pt-Ru/TiO₂/C.     

Ethanol oxidation on novel, carbon supported Pt alloy catalysts—Model studies under defined diffusion conditions

The structure, surface composition and activity/selectivity for ethanol oxidation of carbon supported Pt alloy catalysts with different composition and catalyst loading, which were synthesized via the polyol-route, were investigated and characterized by microscopic/spectroscopic methods (TEM, EDX, XRD) and electrochemical (RDE, on-line DEMS) measurements under well-defined transport and diffusion conditions. The performance of the polyol-type Pt/C (20 wt.%), PtRu/C (20, 40 and 60 wt.%), and Pt₃Sn/C (20 wt.%) catalysts was compared with that of commercial Pt/C, PtRu/C and Pt₃Sn/C (E-Tek) catalysts. The metal particle sizes of the polyol-type catalysts are significantly smaller than those of the corresponding commercial catalysts, nevertheless both the mass specific activities and, more pronounced, the inherent, active surface area specific activities are lower than those of the commercial catalysts, which is related to the lower degree of alloy formation in the polyol-type catalysts. For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under conditions of this study, CO₂ formation contributes by ≤1% for potentiostatic reaction conditions. The lower activity of the polyol-type catalysts is mainly due to the lower activity for acetaldehyde formation. Implications and further strategies for fuel cell applications are discussed.     

The oxidation of carbon monoxide at platinum and gold metallized membrane electrodes

The oxidation of carbon monoxide at gold platinum membrane electrodes is discussed and it is shown that the electrochemical characteristics of these electrodes are similar to massive electrodes. At platinum the short time response is determined by the oxidation of a surface monolayer of carbon monoxide by a reactant pair mechanism occuring at the edges of growing islands of an oxidised platinum species whilst at gold, the process is diffusion controlled. On both metals the longer timescale response is complicated by poisoning of the surface by a reaction intermediate but it is also shown that a gold anode may be reactivated by potential cycling. The relevance of these results to the construction of an analytical device is discussed.     

CO oxidation on Pt supported catalysts. Kinetics and multiple steady states

The conversion of carbon monoxide to carbon dioxide was measured in a recyle reactor automatically controlled by a computer. Two Pt/SiO₂ catalysts of different dispersion were employed. Isothermal experiments (in which the carbon monoxide inlet concentration was varied) and temperature-programmed experiments (in which the temperature was varied) yielded multiple steady states and complete hystereses. The rate data were controlled well by three LHHW kinetic models. However only two of them predicted well the transitions from low to high conversion.     

Effect of carbon surface oxidation on platinum supported carbon particles on the performance of gas diffusion electrodes for the oxygen reduction reaction

The effect of carbon surface oxidation on platinum supported carbon particles (Pt/C) with nitric acid was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, polarization experiments and chronoamperometry. Cyclic voltammograms, polarization curves and electrochemical impedance spectra showed that the treated catalyst had much larger active surface area and higher ionic conductivity than the untreated catalyst, and provided enhanced performance for oxygen reduction. The formation of acidic groups was examined by IR spectra. The Pt/C surface oxidation had a large effect on the performance of a gas diffusion electrode for oxygen reduction reaction.     

Ultra-long Pt nanolawns supported on TiO2-coated carbon fibers as 3D hybrid catalyst for methanol oxidation

In this study, TiO₂ thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO₂, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO₂ is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO₂ hybrid structure.     

PtCo supported on ordered mesoporous carbon as an electrode catalyst for methanol oxidation

A catalyst for methanol oxidation, PtCo supported on graphitized mesoporous carbon, has been synthesized and its electrochemical activity for methanol oxidation has been investigated. The graphitized mesoporous carbon support with ordered pore structure and high surface area of 585 m² g⁻¹ was prepared by one-step melt casting method using Al doped hexagonal mesoporous silica as hard templates and mineral pitches as carbon precursors followed by carbonization at 800 °C. The materials were characterized by X-ray diffraction, Raman spectra, field emission scanning electron microscopy, transmission electron microscopy and nitrogen sorption techniques. Cyclic voltammetry and amperometric i-t tests were adopted to characterize the electro-catalytic activities of the materials for methanol oxidation. The results show that the graphitized mesoporous carbon exhibits large electrochemical capacitance and good electric property. After supported with 20 wt%Pt or 20 wt%PtCo nanoparticles, the resultant mesostructured composites show 26-97% higher electrochemical catalytic activity for methanol oxidation than commercial catalyst 20 wt%Pt/C in mass activity (mA mg Pt⁻¹).     

Kinetic parameters for anodic oxidation of hypochlorite ion on Pt and Pt oxide electrodes in alkaline solution

Kinetic parameters for the anodic oxidation of hypochlorite ion have been determined by means of normal pulse voltammetry by using a platinum disk as the working electrode. By using the working electrode that formed an oxide film by electrochemical pretreatment, the effect of the lattice oxygen of the surface oxide on the reaction was also examined. The measurement results were analyzed by the classical method, and then the analytical results were evaluated by digital simulation. The normal pulse voltammogram of the hypochlorite ion showed quasi-reversible oxidation waves. The apparent rate constant was calculated to be 5.0-8.1 × 10⁻⁴ cm s⁻¹, depending on the electrode surface state. At the low-concentration range of <4.0 mg Cl dm⁻³, the oxidation current was concentration dependent at the cathodically polarized electrode, while it became independent after the anodic polarization.     

Complete oxidation of methane at low temperature over Pt catalysts supported on high surface area SnO2

Topics in Catalysis - The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH4 traces under lean conditions at low temperature was...     

Relationship among the physicochemical properties,electrocatalytic performance and kinetics of carbon supported Pt catalyst for ethanol oxidation

A new carbon supported Pt (Pt/C(b)) catalyst was prepared by reducing H₂PtCl₆ in glycol solution using formic acid as a reducing agent, and has been found in this work to be highly active and stable for the electrochemical oxidation of ethanol. The preparation produces highly dispersed Pt particles, of 2.6 nm average size, and with high electrochemical surface area, 98 m²/g. The apparent activation energy of ethanol oxidation over the Pt/C(b) catalyst electrode is low, 10–14 kJ/mol, over the range of potentials from 0.3 to 0.6 V.     

Electrochemical characterization and reactivity of Pt nanoparticles supported on single-walled carbon nanotubes

Carbon nanotubes have been proposed as advanced metal catalyst support for electrocatalysis. In this paper, Pt nanoparticles supported on single-walled carbon nanotubes (SWCNTs)-Pt, were prepared using a solid-state reaction between the SWCNTs and two different Pt precursors, bis(dibenzylideneacetone)platinum [Pt(DBA)₂] or tri(dibenzylideneacetone)platinum [Pt(DBA)₃]. TEM images of the samples show Pt nanoparticles with a particle size around 2.5 nm with a high degree of dispersion on the SWCNTs. A detailed electrochemical characterization of the surface of the samples including irreversibly adsorbed adatoms of Bi and Ge as probe reactions has been carried out. It has been stated that SWCNTs-Pt samples subjected to the classical electrochemical activation induce a serious sintering of the Pt nanoparticles.