Electrostatic layer-by-layer a of platinum-loaded multiwall carbon nanotube multilayer: A tunable catalyst film for anodic methanol oxidation

A simple layer-by-layer (LBL) electrostatic adsorption technique was developed for deposition of films composed of alternating layers of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged multiwall carbon nanotubes bearing platinum nanoparticles (Pt-CNTs). PDDA/Pt-CNT film structure and morphology up to six layers were characterized by scanning electron microscopy and ultraviolet-visible spectroscopy, showing the Pt-CNT layers to be porous and uniformly deposited within the multilayer films.

Electrodeposition of platinum nanoclusters on type I collagen modified electrode and its electrocatalytic activity for methanol oxidation

We firstly reported a novel polymer matrix fabricated by type I collagen and polymers, and this matrix can be used as nanoreactors for electrodepositing platinum nanoclusters (PNCs). The type I collagen film has a significant effect on the growth of PNCs. The size of the platinum nanoparticles could be readily tuned by adjusting deposition time, potential and the concentration of electrolyte, which have been verified by field-emitted scanning electron microscopy (FE-SEM). Furthermore, cyclic voltammetry (CV) has demonstrated that the as-prepared PNCs can catalyze methanol directly with higher activity than that prepared on PSS/PDDA film, and with better tolerance to poisoning than the commercial E-TEK catalyst. The collagen-polymer matrix can be used as a general reactor to electrodeposit other metal nanostructures.

Green synthesis of highly stable platinum nanoparticles stabilized by amino-terminated ionic liquid and its electrocatalysts for dioxygen reduction and methanol oxidation

Preparation of monodispersed platinum nanoparticles with average size 2.0 nm stabilized by amino-terminated ionic liquid was demonstrated. The resulting platinum nanoparticles (Pt-IL) retained long-term stability without special protection. The Pt-IL nanoparticles exhibited high electrocatalytic activity toward reduction of oxygen and oxidation of methanol. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry confirmed that the Pt-IL films could catalyze an almost four-electron reduction of dioxygen to water.

Effect of pretreatment of black carbon on electrocatalytic activity of Pt/C catalyst for methanol oxidation

Direct methanol fuel cell (DMFC) has attracted wide attention due to its many advantages. However, its practical application is limited by the low electrocatalytic activity of the anodic Pt/C catalyst usually used for the methanol oxidation. In this paper, in order to increase the electrocatalytic performance of the Pt/C catalyst for the methanol oxidation, the black carbon, usually used as the supporter, was pretreated with CO2, air, HNO3 or H2O2. The cyclic voltarnmetric results indicated that the current densities of the anodic peak of methanol oxidation at the Pt/C catalysts with the black carbon pretreated with CO2,air, HN03, H202 and untreated black carbon were 39, 33, 32, 20 and 18 mA center dot cm(-2), respectively, illustrating that among the above five kinds of the Pt/C catalysts, the Pt/C catalyst with the black carbon pretreated with CO2 shows the best electrocatalytic activity and stability for the methanol oxidation. Its main reason is that the CO2 pretreatment could reduce the content of the oxygen-containing groups on the surface of the black carbon and increase the content of graphite in the black carbon, leading to the low resistance of the black carbon and the increase in the dispersion extent of the Pt particles in the Pt/C catalyst.

Electrooxidation of COad intermediated from methanol oxidation on polycrystalline Pt electrode

The poisonous intermediate of methanol oxidation on a Pt electrode was validated to be COad by electrochemical method. An approximate treatment to bimolecular elementary reactions on an electrode was advanced and then was applied to the stripping normal pulse voltammetry (NPV) for complex multistep multielectron transfer processes on plane electrodes to study the kinetics of completely irreversible process Of COad oxidation to CO2. The kinetic parameters for this process, such as standard rate constant (0) and anodic transfer coefficient (alpha) for this irreversible heterogeneous electron-transfer process at electrode/solution interface and apparent diffusion coefficient (D-app) for charge-transfer process within the monolayer of COad on electrode surface, were obtained with stripping NPV method. The effect of the approximate treatment on the kinetic parameters was also analyzed.

Preparation of a carbon supported Pt catalyst using an improved organic sol method and its electrocatalytic activity for methanol oxidation

The organic sol method for preparing ultrafine transition metal colloid particles reported for the first time by Bonnemann et al. [H. Bonnemann, W Brijoux, R. Brinkmann, E. Dinjus, T. Jou beta en, B. Korall, Angew. Chem. Int. Ed. Engl., 30 (1991) 1312] has been improved in this paper. The improved organic sol method uses SnCl2 as the reductant and methanol as the organic solvent. Thus, this method is very simple and inexpensive. It was found that the average size of the Pt particles in the Pt/C catalysts can be controlled by adjusting the evaporating temperature of the solvent. Therefore, the Pt/C catalysts prepared by the same method are suitable for evaluating the size effect of the Pt particles on electrocatalytic performance for methanol oxidation. The results of the X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that when the evaporating temperatures of the solvent are 65, 60, 50, 40, and 30 degrees C, the average sizes of the Pt particles in the Pt/C catalysts prepared are: 2.2, 3.2, 3.8, 4.3, and 4.8 nm, respectively. The X-ray photoelectron spectroscopic (XPS) results demonstrated that the small Pt particles are easily oxidized and the decomposition/adsorption of methanol cannot proceed on the surfaces of Pt oxides.

Effect of cations in solution on the oxidation of methanol on the surface of platinum electrode

The effect of metal cations in solution on the oxidation of methanol on the electrode surface of platinum is a neglected aspect to direct methanol fuel cell (DMFC). In this paper, a smooth platinum electrode absorbing metal cations as the working electrode was applied to investigate the methanol oxidation with the cyclic voltammetry (CV) in 1.0 mol L-1 H2SO4. From the analysis of experiment, it is found that the cations, Li+, Ce4+, Mn2+, Ni2+, Cu2+, have some negative effect on the catalytic oxidation of methanol on the surface of platinum. The degree of the effect from different cations was analyzed.

Physical and electrochemical characterizations of PtRu/C catalysts by spray pyrolysis for electrocatalytic oxidation of methanol

In this paper, it was reported that the carbon-supported Pt-Ru(Pt-Ru/C) catalyst used as the anodic catalyst in the direct methanol fuel cell (DMFC) was synthesized with a two-step spray pyrolysis (SP) method using the Pt and Ru metal salt as the precursors and polyethylene glycol (PEG) with the different molecular weights (Mw= 200,600,and 1000 analytical reagent) as cosolvent. PEG as a cosolvent plays a crucial role in producing PtRu/C catalysts. It was found that the Mw of PEG could affect the electrocatalytic activity of Pt-Ru and the morphology of the Pt-Ru particles in the Pt-Ru/C catalysts prepared with this method. When the Mw of PEG is 600, the Pt-Ru particles in the Pt-Ru/C catalyst prepared with this method possess the small average size, narrow size distribution, uniform dispersion, and high electrochemically active specific surface area. The electrocatalytic activity of the Pt-Ru/C catalyst prepared with this method using the cosolvent PEG with Mw = 600 for the methanol oxidation is much higher than that of the commercial E-TEK Pt-Ru/C catalyst. Therefore, the two-step SP method is an excellent method for the preparation of the Pt-Ru/C catalyst used in DMFCs.

Electrocatalytic performance of Pt-TiO2/C complex catalysts for oxidation of methanol

It is reported for the first time that the Pt-TiO2/C catalyst prepared with chemical reduction and sol-gel method showed the excellent electrocatalytic activity and stability for the electrooxidation of methanol. When the atom ratio of Ti to Pt in the catalysts is 1/2, the catalysts showed the best electrocatalytic properties. After the catalyst is treated at 500 degreesC, the performance is further improved. It is hopeful to use the catalyst in the pratical DMFC.

Promoter effects of rare earth ions on electrocatalytic oxidation of methanol

The promoter effects of rare earth ions on the electrocatalytic oxidation of methanol at the Pt electrode were studied using the cyclic voltammetry and stable polarization techniques. It was found for the first time that Eu, Ho, Dy ions could accelerate the electrocatalytic oxidation of methanol at the Pt electrode, while Lu, Pr, Yb, Sm ions showed inhibitor effects.

Studies on electrocatalytic performance of titanium oxide electrode modified with Pt toward the oxidation of methanol

Electrocatalytic performance of the Pr-TiOx/Ti electrode prepared with electrochemical reduction-oxidation method toward the oxidation of methanol has been studied, The experimental results showed that the Pt-TiOx/Ti electrode has a high electrocatalytic activity and good stability for the electrocatalytic oxidation of methanol, By means of electrochemical, XPS, STM and in-situ FTIR techniques, it was found that one reason for the electrode to exhibit an excellent performance is attributed to the high dispersion between nanosized Pt and TiOx particles, The low adsorption ability of the intermediate derived from methanol, such as linearly adsorbed CO species on the electrode surface due to the interaction between Pt and TiOx, also results in the excellent performance.

Electrocatalytic oxidation of methanol at the titanium oxide electrode modified with Pt microparticles

The electrocatalytic oxidation of methanol at the Titanium oxide (TiOx, x<2) film modified with Pt microparticles has been studied. The results show that the modified electrodes exhibit a significant electrocatalytic activity and good stability for the oxidation of methanol. Under the optimal conditions, the peak current density at 0.58 V for the oxidation of methanol in the positive-going sweep is about 526 mA/cm(2) at the scan rate of 5 mV/s in 0.5 mol/L CH3OH and 0.5 mol/L H2SO4 solution and the over potential of the methanol oxidation at the modified electrode increases about 30 similar to 40 mV after 70 minutes at the current density of 100 mA/cm(2) and 50 mA/cm(2). The enhanced electrocatalytic activity and good stability are ascribed to the high dispersion of Pt microparticles in and on the TiOx film and the synergistic effect between Pt microparticles and TiOx.