Optimization of platinum dispersion in Pt–PEM electrodes: application to the electrooxidation of ethanol

Nafion® can be used as a solid polymer electrolyte in a PEM fuel cell. Direct platinization of the membrane was realized by chemical reduction of a platinum compound. The platinization procedure was modified to enhance the roughness factor and thus to improve the electrocatalytic activity towards ethanol electrooxidation. The Pt–PEM electrodes were characterized by TEM, atomic absorption analysis, cyclic voltammetry and their polarization curves for ethanol electrooxidation.     

Enhancement of the electrooxidation of ethanol on a Pt–PEM electrode modified by tin. Part I: Half cell study

The direct platinisation of a solid polymer electrolyte (Nafion^® membrane) was realized by chemical reduction of a platinum salt. The Pt–PEM electrodes thus obtained were modified by tin to improve the electrocatalytic activity towards the electrooxidation of ethanol. The Pt–PEM and Pt–Sn–PEM electrodes were characterized by TEM, EDX and XRD analysis, cyclic voltammetry, and their polarisation curves for the electrooxidation of ethanol were determined under quasisteady state conditions.     

Waterborne hybrid alkyd–acrylic dispersion: Optimization of the composition using mixture experimental designs

VOC-free waterborne hybrid alkyd–acrylic (50/50 wt/wt) dispersions were synthesized by melt condensation reactions between acrylic pre-polymers bearing carboxylic groups and medium-oil alkyd resins, followed by a self-emulsification through the neutralization of the carboxylic groups by an aqueous ammonia solution. A mixture experimental design was used to investigate how formulation components of the hybrid alkyd–acrylic resin affect the properties of the hybrid dispersion in terms of the viscosity of the dispersion, particle size, hydrolytic stability, and coating performance, namely gloss and film hardness. It was found that the content of ionizable monomers is the dominant factor controlling the particle size. This latter was shown to meaningfully affect the gloss of the coating after drying. The viscosity of the dispersion was mainly governed by the content of the soybean oil fatty acid which also controlled the hardness of the coating film after drying. An optimal composition that fits the requirement of paint formulation in terms of particle size, viscosity, hardness, and gloss was defined on the basis of the results of the mixture experimental design.     

Synergistic bimetallic Ru–Pt catalysts for the low-temperature aqueous phase reforming of ethanol

Aqueous phase reforming (APR) of ethanol has been studied over a series of Ru and Pt catalysts supported on carbon and titania, with different metal loadings and particle sizes. This study proposed that, on both metals, ethanol is first dehydrogenated to acetaldehyde, which subsequently undergoes C C cleavage followed by different paths, depending on the catalyst used. For instance, although monometallic Pt has high selectivity toward H₂ via dehydrogenation, it has a low efficiency for C C cleavage, lowering the overall H₂ yield. Large Ru particles produce CH₄ through methanation, which is undesirable because it consumes H₂. Small Ru particles have lower activity but higher selectivity toward H₂ rather than CH₄. On these small particles, CO blocks low-coordination sites, inhibiting methanation. The combination of the two metals in bimetallic Ru–Pt catalysts results in improved performance, benefiting from the desirable properties of each Ru and Pt, without the negative effects of either. © 2018 American Institute of Chemical Engineers AIChE J, 65: 151–160, 2019     

Electrooxidation of C1 to C3 alcohols with Pt and Pt–Ru sputter deposited interdigitated array electrodes

The electrooxidation of methanol, ethanol, and 2-propanol was investigated with interdigitated array electrodes (IDAEs). The IDAE oxidizes alcohol at the generator and reduces the reaction intermediates produced by the oxidation process at the collector. Thus, the reaction intermediates can be estimated with the IDAE. The IDAE in the present work was made of sputter deposited Pt and Pt–Ru. The use of Ru free and added electrodes provides information on the effect of Ru addition on the alcohol oxidation. Cyclic voltammetric analyses revealed that Ru addition enhances the oxidation currents and reduces the E_onset of the alcohols. The detectable reaction intermediate at the methanol and ethanol oxidation was proton, while the intermediate species was acetone in 2-propnaol oxidation.     

Substrate transformation phenomena during the nucleation of silver on polyfaced platinum single crystal electrodes—II. Characterization of the platinum surface

The electrochemical behaviour of the polyfaced platinum single crystal electrodes is studied by means of combined voltammetric and pulse potentiostatic methods. Information is obtained about the specific transformations of the platinum surface caused by temperature and polarization treatments typical for the nucleation pulse experiments.     

Predicting the diameters of droplets produced in turbulent liquid–liquid dispersion

The droplet size distribution in liquid–liquid dispersions is a complex convolution of impeller speed, impeller type, fluid properties, and flow conditions. In this work, we present three a priori modeling approaches for predicting the droplet diameter distributions as a function of system operating conditions. In the first approach, called the two-fluid approach, we use high-resolution solutions to the Navier–Stokes equations to directly model the flow of each phase and the corresponding droplet breakup/coalescence events. In the second approach, based on an Eulerian–Lagrangian model, we describe the dispersed fluid as individual spheres undergoing ongoing breakup and coalescence events per user-defined interaction kernels. In the third approach, called the Eulerian–Parcel model, we model a sub-set of the droplets in the Eulerian–Lagrangian model to estimate the overall behavior of the entire droplet population. We discuss output from each model within the context of predictions from first principles turbulence theory and measured data.     

Copolymerization in dispersion of divinyl benzene–maleic anhydride in the presence of silylated montmorillonite clays

Sodium montmorillonite (NaMMT clay) derivatives were encapsulated in polymer particles obtained through dispersion copolymerization of divinyl benzene (DVB) with maleic anhydride (MA). To evidence the effect of alkyl monoalkoxysilanes upon MMT reaction, a variety of MMT clay functional derivatives were investigated. Particles with an increased size of modified MMT clay dispersed in dichloromethane were obtained using alkyl monoalkoxysilanes with a longer hydrocarbon chain. Relatively long hydrocarbon chains can exhibit a low substitution degree of MMT clay with alkyl monoalkoxysilanes. MMT class with a low substitution degree leads in the presence of alkoxysilanes to particles with average size between 700 and 1200 nm, and when DVB–MA copolymer is added the particles size decreases (~480 nm). The influence of layered silicates on the thermal stability of DVB–MA copolymer as a function of the used vinyl siloxanes derivatives for functionalization of MMT, on one hand, and the nonlinear variation of refractive index of used silanes on the other hand, pointing out the autoassociation during initial reaction of substitution.     

Overcoming the quality–quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion–extraction process

Dispersion-printing processes are essential for the fabrication of various devices using carbon nanotubes (CNTs). Insufficient dispersion results in CNT aggregates, while excessive dispersion results in the shortening of individual CNTs. To overcome this tradeoff, we propose here a repetitive dispersion–extraction process for CNTs. Long-duration ultrasonication (for 100 min) produced an aqueous dispersion of CNTs with sodium dodecylbenzene sulfonate with a high yield of 64%, but with short CNT lengths (a few μm), and poor conductivity in the printed films (∼450 S cm⁻¹). Short-duration ultrasonication (for 3 min) yielded a CNT dispersion with a very small yield of 2.4%, but with long CNTs (up to 20–40 μm), and improved conductivity in the printed films (2200 S cm⁻¹). The remaining sediment was used for the next cycle after the addition of the surfactant solution. 90% of the CNT aggregates were converted into conductive CNT films within 13 cycles (i.e., within 39 min), demonstrating the improved conductivity and reduced energy/time requirements for ultrasonication. CNT lines with conductivities of 1400–2300 S cm⁻¹ without doping and sub-100 μm width, and uniform CNT films with 80% optical transmittance and 50 Ω/sq sheet resistance with nitric acid doping were obtained on polyethylene terephthalate films.     

Optimization and modeling of the performance of polydimethylsiloxane for pervaporation of ethanol−water mixture

Response surface methodology was used to optimize the performance of pervaporation of ethanol aqueous solution using polydimethylsiloxane hollow-fiber membrane. The effects of four operating conditions, that is, the feed temperature (30–50°C), the feed flow rate (10–50 L/h), ethanol concentration (5–20 wt%), and the vacuum pressure (10–50 KPa) on the membrane selectivity and the total flux of permeation were investigated with response surface methodology. The results showed that a quadratic model was suggested for both selectivity and total flux showing a high accuracy with R² = 0.9999 and 0.9995, respectively. The developed models indicated a significant effect of the four studied factors on both selectivity and total flux with some significant interactions between these factors. The optimum selectivity was 15.56, achieved for a feed temperature of 30°C, feed flow rate of 10 L/h, ethanol concentration of 15 wt%, and a permeate pressure of 10.74 KPa whereas the optimum total flux was 1833.66 g/m².h was observed for at a feed temperature of 50°C, a feed flow rate of 50 L/h, ethanol concentration of 15 wt%, and a permeate pressure of 49.38 KPa.     

Evaluation of the surface roughness of microporous Ni–Zn–P electrodes by in situ methods

The surface roughness of porous Ni–Zn–P electrodes was studied in 1 M NaOH using in situ electrochemical techniques: ratio of the polarization current densities, electrochemical impedance spectroscopy, cyclic voltammetry, coulometric oxidation of the surface, and a new technique of a CO molecular probe. The obtained surface roughness was about 5.5 × 10³. Good agreement was observed between the results obtained by all these techniques.     

The function of zeolite on Pt autoreduction and dispersion in Pt/L and Pt/β catalysts

TPR, CO-FTIR and¹²⁹Xe NMR spectroscopic techniques were used to measure the distribution of platinum species after the calcination of Pt/L and Pt/ zeolites. Autoreduction which occurred in Pt/ zeolite was avoided in the channel of L zeolite. Pt particles dispersed well and exhibited excellent reactivity for the aromatization ofn-hexane in L zeolite.     

Effect of MEA fabrication techniques on the cell performance of Pt–Pd/C electrocatalyst for oxygen reduction in PEM fuel cell

The effect of three different membrane electrode assembly (MEA) fabrication techniques, catalyst-coated substrate by direct spray (CCS) and catalyst-coated membrane by direct spray (CCM-DS) or decal transfer (CCM-DT), on the performance of oxygen reduction in a proton exchange membrane (PEM) fuel cell was carried out under identical conditions of Pt–Pd/C electrocatalyst loading. The results indicated that the fabrication technique had only a very slight effect on the ohmic resistance of the PEM fuel cell but it significantly affected the charge transfer resistance and open circuit voltage (OCV). The cells prepared by the CCM method, and particularly by decal transfer, exhibited a significantly higher OCV but a lower ohmic and charge transfer resistance compared with the other investigated fabrication techniques. By using cyclic voltammetry with H₂ adsorption, it was found that the electrochemical active area of the electrocatalyst prepared by CCM-DT was higher than those prepared by CCS and CCM-DS by around 1.76- and 1.05-fold, respectively. Under a H₂/O₂ system at 0.6 V, the cells with MEA made by CCM-DT provided the highest cell performance of around 350 mA/cm², significantly greater than those prepared by the CCS and CCM-DS (149 and 42 mA/cm², respectively).     

Electrocatalytic oxidation of 1,2-propanediol—II. Behaviour of platinum ad-atom electrodes in alkaline medium

The electrocatalytic oxidation of 1,2-propanediol is studied in alkaline medium, both on pure Pt, and on ad-atom modified Pt electrodes.All the five metal ad-atoms investigated here (Bi, Cd, Pb, Re, Tl) enhance the electrocatalytic activity of Pt without inhibiting the overall process, conversely to that observed in acid medium. Bi ad-atoms, and particularly Pb and Tl ad-atoms, greatly increase the oxidation rate leading to enhancement factors of about 60 at low overvoltages. Cd ad-atoms shift negatively the polarization curves., giving an enhancement factor of about 25 at low potentials, whereas Re ad-atoms have only a slight positive effect (enhancement factor below two).An explanation, based on the bifunctional theory of electrocatalysis, is suggested to interpret these enhancement effects.     

A comparative study of Pd/rGO and Pd–Cu/rGO toward electrooxidation of low ethanol concentrations for fuel cell-based breath alcohol analyzer application

Journal of Applied Electrochemistry - The purpose of this work is activity evaluation of optimized Pd–Cu/rGO as an anode catalyst for electrooxidation of low ethanol concentrations...     

What is the state of aggregation of ethanol molecules in ethanol–supercritical carbon dioxide mixtures? An FTIR investigation in the full molar fraction range

The evolution of the degree of hydrogen bonding of ethanol molecules in scCO₂–ethanol mixtures for different molar fraction (from 0.5 to 100% in ethanol) in the temperature range 40–200 °C and at two different constant pressures P = 15 and 20 MPa is reported in this paper. For a given pressure, we observe a strong dependence of the degree of hydrogen bonding as a function of temperature and ethanol molar fraction. We emphasize that a detailed knowledge of the degree of hydrogen bonding of ethanol molecules in these binary systems is important for the understanding and the further development of the supercritical fluid technology.     

Elucidating the thermal degradation of carbazole-containing platinum–polyyne polymers

In this article, we present the significant influence of the substitution pattern of carbazole on the thermal stability of carbazole-containing platinum(II)–polyyne polymers. A series of the studies on the dynamic and isotherm conditions revealed a better thermal stability for the 3,6-carbazole based platinum(II)–polyyne polymer (36CbzPtP), where alkynes were located at the p-phenylene positions relative to the carbazole nitrogen atom, compared to that for the 2,7-carbazole based counter polymer (27CbzPtP), where the alkynes were located at the m-phenylene positions relative to the carbazole nitrogen atom. On the other hand, the thermogravimetry–mass spectrometry–Fourier transform infrared technique applied to the two polymers revealed the same degradation mechanism, which probably involved the thermal decomposition of triethyl phosphine moieties and which was followed by the C C scission of hexadecyl chains. The carbazole moieties eventually underwent degradation when the temperature exceeded 415 °C. Molecular modeling showed that polymer 27CbzPtP formed a linear structure, whereas polymer 36CbzPtP adopted a curved structures; this led to different packing modes of the polymer chains. This structural difference affected the efficiency of the initial degradation event of the triethyl phosphine groups. The curved structures of 36CbzPtP sterically protected the triethyl phosphine groups; this led to an increased thermal stability over that of 27CbzPtP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47639.     

Influence of the crystalline structure of ZrO2 on the metallic properties of Pt in Pt/WO3–ZrO2 catalysts

The influence of the crystalline structure of ZrO₂ on the metallic properties of Pt, when supported on WO₃–ZrO₂, was studied. Pt supported on tetragonal zirconia loses its metallic properties while when supported on monoclinic zirconia it presents good metallic activities. WO₂,^2- deposited on amorphous Zr(OH)₄ before calcination generates an active material for n‐butane isomerization. The larger the fraction of the tetragonal phase of zirconia in this material, the higher the isomerization activity and the lower the metallic activity of Pt. This revised version was published online in July 2006 with corrections to the Cover Date.