Tuning of size and shape of Au–Pt nanocatalysts for direct methanol fuel cells

In this article, we report the precise control of the size, shape, and surface morphology of Au–Pt nanocatalysts (cubes, blocks, octahedrons, and dogbones) synthesized via a seed-mediated approach. Gold “seeds” of different aspect ratios (1–4.2), grown by a silver-assisted approach, were used as templates for high-yield production of novel Au–Pt nanocatalysts at a low temperature (40 °C). Characterization by electron microscopy (SEM, TEM, HRTEM), energy dispersive X-ray analysis, UV–Vis spectroscopy, zeta-potential (surface charge), atomic force microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry were used to better understand their physico-chemical properties, preferred reactivities and underlying nanoparticle growth mechanism. A rotating disk electrode was employed to evaluate the Au–Pt nanocatalysts electrochemical performance in the oxygen reduction reaction (ORR) and the methanol oxidation reaction of direct methanol fuel cells. The results indicate the Au–Pt dogbones are partially and in some cases completely unaffected by methanol poisoning during the evaluation of the ORR. The ORR performance of the octahedron particles in the absence of MeOH is superior to that of the Au–Pt dogbones and Pt-black; however, its performance is affected by the presence of MeOH.     

Nuclear power plant types and the management of plutonium and minor actinides – in search of fuel cycle flexibility

Transuranics management concerns all NPP types, because of the specifications for a sustainable development. Multiple recycling is mandatory. Neutronic abundance can be obtained in fast spectrum, or by adding external neutrons or (temporarily) with additional ²³⁵U. The LWRs can control the plutonium inventory and significantly reduce the amount of transuranics transferred to the geological repository, thanks to the use of innovative nuclear fuel in a limited part of the NPP fleet. HTR adapted to transuranics burning can help. In the future, in addition to the liquid metal FBR, a strategy based on a gas cooled technological line and advanced fuel opens a second path towards fast spectra. Strategies for defining the optimal mix of reactor types in the nuclear fleet at a given time and demonstrating the fuel cycle flexibility are under study. To cite this article: J.-B. Thomas, C. R. Physique 3 (2002) 783–796.     

Simultaneous flow field and fuel concentration imaging at 4.8 kHz in an operating engine

High-speed particle image velocimetry (PIV) and planar laser induced fluorescence (PLIF) techniques are combined to acquire flow field and fuel concentration in a spray-guided spark-ignited direct-injection (SG-SIDI) engine under motored and fired operation. This is a crucial step to enable studies that seek correlations between marginal engine operation (misfires or partial burns) and local, instantaneous mixture and flow conditions. Correlated flow and fuel data are extracted from a 4 mm×4 mm sub-region directly downstream the spark plug to characterize the in-cylinder conditions next to the spark plug during the spray and ignition event. Values of equivalence ratio, velocity magnitude, shear strain rate, and vorticity all increase during the spray event and decrease an order of magnitude during the duration of the spark event.     

Effects of pressure and fuel dilution on coflow laminar methane–air diffusion flames: A computational and experimental study

In this study, the influence of pressure and fuel dilution on the structure and geometry of coflow laminar methane–air diffusion flames is examined. A series of methane-fuelled, nitrogen-diluted flames has been investigated both computationally and experimentally, with pressure ranging from 1.0 to 2.7 atm and CH₄ mole fraction ranging from 0.50 to 0.65. Computationally, the MC-Smooth vorticity–velocity formulation was employed to describe the reactive gaseous mixture, and soot evolution was modelled by sectional aerosol equations. The governing equations and boundary conditions were discretised on a two-dimensional computational domain by finite differences, and the resulting set of fully coupled, strongly nonlinear equations was solved simultaneously at all points using a damped, modified Newton's method. Experimentally, chemiluminescence measurements of CH* were taken to determine its relative concentration profile and the structure of the flame front. A thin-filament ratio pyrometry method using a colour digital camera was employed to determine the temperature profiles of the non-sooty, atmospheric pressure flames, while soot volume fraction was quantified, after evaluation of soot temperature, through an absolute light calibration using a thermocouple. For a broad spectrum of flames in atmospheric and elevated pressures, the computed and measured flame quantities were examined to characterise the influence of pressure and fuel dilution, and the major conclusions were as follows: (1) maximum temperature increases with increasing pressure or CH₄ concentration; (2) lift-off height decreases significantly with increasing pressure, modified flame length is roughly independent of pressure, and flame radius decreases with pressure approximately as P^?1/2; and (3) pressure and fuel stream dilution significantly affect the spatial distribution and the peak value of the soot volume fraction.     

Rhenium oxide nanoparticles – Sonochemical synthesis and integration on anode powders for solid oxide fuel cells

Rhenium oxide nanoparticles have been prepared using ultrasonication at 20 kHz. Samples characterization was committed via SEM-EDX, TEM, XRD, and Raman spectroscopy. Various experimental parameters were examined, including precursor/substrate amounts, ultrasonication intensity, and type of solvent used. Insights to the agglomeration of the prepared nanoparticles depending on the preparation parameters are given. As ultrasonic source we used either an ultrasonic probe by Sonics & Materials Inc. (20 kHz, 750 W net output) or a Bandelin SONOPULS HD 3200 ultrasound generator (20 kHz, 200 W net output) at intensities between 30 and 100 W/cm². The rhenium oxide nanoparticles haven been decorated on state-of-the-art anode materials (NiO/GDC) for solid oxide fuel cells (SOFCs) in order to prepare catalytically more active anode powders. These experiments revealed that ultrasonication intensity and solvents used are able to affect final nanoparticles size distribution and morphology. At the same time, ratio of precursor and substrate compounds amounts as well as ultrasonication intensity and duration were all found to affect the decoration loading extend of nanoformations on substrate powders. The results showing the influence of the above-mentioned parameters allowed for the quantification of the effects on the loading and the preferable sites of the decoration.     

Heat and mass transfer in a coal-water fuel particle at the stage of “thermal” treatment

The problem of heat and mass transfer has been solved numerically under the conditions of coal-water fuel particle ignition. The concurrent processes of evaporation, filtration of steam, thermal decomposition of the organic part of coal, thermal and chemical interaction of steam and coke carbon, and oxidation of products of their reaction and volatiles by the external oxidizer have been taken into account. The scales of influence of individual thermophysical and thermochemical properties of coals on the characteristics and conditions of ignition of coal-water slurry have been determined.     

Modelling biodiesel–diesel spray combustion using multicomponent vaporization coupled with detailed fuel chemistry and soot models

A multicomponent vaporization model is integrated with detailed fuel chemistry and soot models for simulating biodiesel–diesel spray combustion. Biodiesel, a fuel mixture comprised of fatty-acid methyl esters, is an attractive alternative to diesel fuel for use in compression-ignition engines. Accurately modelling of the spray, vaporization, and combustion of the fuel mixture is critical to predicting engine performance using biodiesel. In this study, a discrete-component vaporization model was developed to simulate the vaporization of biodiesel drops. The model can predict differences in the vaporization rates of different fuel components. The model was validated by use of experimental data of the measured biodiesel drop size history and spray penetration data obtained from a constant-volume chamber. Gas phase chemical reactions were simulated using a detailed reaction mechanism that also includes PAH reactions leading to the production of soot precursors. A phenomenological multi-step soot model was utilized to predict soot emissions from biodiesel–diesel combustion. The soot model considered various steps of soot formation and destruction, such as soot inception, surface growth, coagulation, and PAH condensation, as well as oxidation by oxygen and hydroxyl-containing molecules. The overall numerical model was validated with experimental data on flame structure and soot distributions obtained from a constant-volume chamber. The model was also applied to predict combustion, soot and NOx emissions from a diesel engine using different biodiesel–diesel blends. The engine simulation results were further analysed to determine the soot emissions characteristics by use of biodiesel–diesel fuels.     

Effect of fuel on the formation structure,transport and magnetic properties of LaMnO3+ δ nanopowders

Single-step low-temperature solution combustion (LCS) synthesis was adopted for the preparation of LaMnO_{3+ δ} (LM) nanopowders. The powders were well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), surface area and Fourier transform infrared spectroscopy (FTIR). The PXRD of as-formed LM showed a cubic phase but, upon calcination (900°C, 6 h), it transformed into a rhombohedral phase. The effect of fuel on the formation of LM was examined, and its structure and magnetoresistance properties were investigated. Magnetoresistance (MR) measurements on LM were carried out at 0, 1, 4 and 7 T between 300 and 10 K. LM (fuel-to-oxidizer ratio; ψ = 1) showed an MR of 17% at 1 T, whereas, for 4 and 7 T, it exhibited an MR of 45 and 55%, respectively, near the T _M-I. Metallic resistivity data below T _M-I showed that the double exchange interaction played a major role in this compound. It was interesting to observe that the sample calcined at 1200°C for 3 h exhibited insulator behavior.     

One-step sonochemical syntheses of Ni@Pt core–shell nanoparticles with controlled shape and shell thickness for fuel cell electrocatalyst

We demonstrate a facile one-step method to synthesize Ni@Pt core–shell nanoparticles (NPs) with a control over the shape and the Pt-shell thickness of the NPs. By adjusting the relative reactivity of the Pt and Ni reagents in ultrasound-assisted polyol reactions, two Ni@Pt NP samples of the same composition (Ni/Pt = 1) and size (3–4 nm) but with different particle shape (octahedral vs. truncated octahedral) and different Pt-shell thicknesses (1–2 vs. 2–3 monolayer) are obtained. The control is achieved by using different Ni reagents, Ni(acac)₂ (acac = acetylacetonate) and Ni(hfac)₂ (hfac = hexafluoroacetylacetonate). A reaction mechanism that can explain all of the observations is proposed. The Ni@Pt NPs show up to threefold higher mass activity than pure Pt NPs in oxygen reduction reaction. Between the two Ni@Pt NP samples, the one composed of octahedral NPs with the thicker Pt-shell has higher activity than the other.     

Simultaneous 36 kHz PLIF/chemiluminescence imaging of fuel,CH2O and combustion in a PPC engine

The requirements on high efficiency and low emissions of internal combustion engines (ICEs) raise the research focus on advanced combustion concepts, e.g., premixed-charge compression ignition (PCCI), partially premixed compression ignition (PPCI), reactivity controlled compression ignition (RCCI), partially premixed combustion (PPC), gasoline compression ignition (GCI) etc. In the present study, an optically accessible engine is operated in PPC mode, featuring compression ignition of a diluted, stratified charge of gasoline-like fuel injected directly into the cylinder. A high-speed, high-power burst-mode laser system in combination with a high-speed CMOS camera is employed for diagnostics of the autoignition process which is critical for the combustion phasing and efficiency of the engine. To the authors’ best knowledge, this work demonstrates for the first time the application of the burst-system for simultaneous fuel tracer planar laser induced fluorescence (PLIF) and chemiluminescence imaging in an optical engine, at 36?kHz repetition rate. In addition, high-speed formaldehyde PLIF and chemiluminescence imaging are employed for investigation of autoignition events with a high temporal resolution (5 frames/CAD). The development of autoignition together with fuel or CH₂O distribution are simultaneously visualized using a large number of consecutive images. Prior to the onset of combustion the majority of both fuel and CH₂O are located in the recirculation zone, where the first autoignition also occurs. The ability to record, in excess of 100 PLIF images, in a single cycle brings unique possibilities to follow the in-cylinder processes without the averaging effects caused by cycle-to-cycle variations.     

Evaluation and optimization of SrCo0.9Ta0.1O3−δ perovskite as cathode for solid oxide fuel cells

The SrCo_0.9Ta_0.1O_3-δ (SCT) perovskite-type oxide is synthesized by the conventional solid state reaction method and examined as an alternative cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The electrical conductivity of SCT sample reaches 250–152 S cm^?1 in the temperature range 600–800 °C. SCT exhibits good chemical compatibility with the intermediate-temperature electrolyte material Sm_0.2Ce_0.8O_1.9 (SDC). The average thermal expansion coefficient of SCT is 21.4 × 10^?6 K^?1. The cathode area specific resistance (ASR) of SCT is only 0.095 Ω cm² at 750 °C and it decreases to 0.068 Ω cm² when SDC is added to form a SCT-SDC composite cathode. The results indicate that the SCT can be a promising alternative cathode material for IT-SOFCs.     

Synthesis and characterization of Pt–Sn–Ce/MC ternary catalysts for ethanol oxidation in membraneless fuel cells

The present work represents the mesoporous carbon-supported Pt–Sn and Pt–Sn–Ce catalysts with different mass ratios have been prepared by co-impregnation reduction method. The prepared catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) investigation. The XRD patterns of prepared Pt/MC (100) Pt–Sn/MC (75:25), Pt–Ce/MC (75:25), and Pt–Sn–Ce/MC (75:20:05) catalysts showed that Pt metal was the predominant material in all the samples, with peaks attributed to the face-centered cubic (fcc) crystalline structures. Additionally changes in the lattice parameters observed for Pt suggest the incorporation of Sn into the Pt crystalling structure with the formation of an alloy mixture with the SnO₂ phase. The TEM analysis designates that the prepared catalysts had similar particle morphology, and their particle sizes were 2–5 nm. The electrochemical studies showed that ternary catalyst shows best performance for oxidation of ethanol molecule at normal temperature. The enhanced ethanol oxidation activity for the ternary Pt–Sn–Ce catalyst is mainly attributed to the synergistic effect of bifunctional mechanism with electronic effect. Additionally, chemical nature of ceria affords oxygen-containing molecule to oxidize acetaldehyde to acetic acid. In this present context, 1 M ethanol was used as a fuel, 0.1 M sodium perborate was used as an oxidant, and 0.5 M sulfuric acid was used as an electrolyte. In mesoporous carbon-supported binary Pt–Sn and ternary Pt–Sn–Ce anode catalysts were effectively tested in a single membraneless fuel cell at normal temperature. The presence of Sn and Ce enhances the CO oxidation; they produced an oxygen-containing species to oxidize acetaldehyde to acetic acid.     

Darrieus–Landau instability of premixed flames enhanced by fuel droplets

Recent experiments on spray flames propagating in a Wilson cloud chamber have established that spray flames are much more sensitive to wrinkles or corrugations than single-phase flames. To propose certain elements of explanation, we numerically study the Darrieus–Landau (or hydrodynamic) instability (DL-instability) developing in premixtures that contain an array of fuel droplets. Two approaches are compared: numerical simulation starting from the general conservation laws in reactive media, and the numerical computation of Sivashinsky-type model equations for DL-instability. Both approaches provide us with results in deep agreement. It is first shown that the presence of droplets in fuel–air premixtures induces initial perturbations which are large enough to trigger the DL-instability. Second, the droplets are responsible for additional wrinkles when the DL-instability is developed. The latter wrinkles are of length scales shorter than those of the DL-instability, in such a way that the DL-unstable spray flames have a larger front surface and therefore propagate faster than the single-phase ones when subjected to the same instability.     

Ignition of a floating droplet of organic coal–water fuel

The results of experimental investigations are presented for the ignition of droplets (particles) of organic coal–water fuels (OCWFs) floating in a flow of an oxidizer using a special combustion chamber from high-temperature quartz glass. The temperature and the velocity of motion of the oxidizer vary in the ranges of 500–900 K and 0.5–3 m/s. The initial sizes (radii) of fuel droplets amounted to 0.3–1.5 mm. As the basic OCWF components, particles (of 80–100 µm in size) of brown coal “B2,” water, mazut, and waste castor and compressor oils are used. With use of the system of high-velocity video registration, the conditions providing for floating of OCWF particles without initiation of burning and with the subsequent steady ignition are established. Four modes of OCWF-droplet ignition with different trajectories of their motion in the combustion chamber are singled out. The times of the OCWF-ignition delay in dependence on the size of fuel particles and oxidizer temperatures are determined. The deviations of the OCWF-ignition-delay times obtained under conditions of suspension of a droplet on the thermocouple junction and while floating in the oxidizer flow are established.     

Evaluation of the neutron production rate using D–D and D–T fuel in an inertial electrostatic confinement fusion device

The correlation between the neutron production rate and fuel species in a spherical inertial electrostatic confinement fusion (IECF) device is investigated by solving the Poisson equation for various ion and electron distribution functions. The fuel ion energy distribution function is determined at each radial point. The fusion reaction rate is evaluated from the energy distribution function. The dependence of the neutron production rate (NPR) on some important parameters, like the ion convergence, the broadening of the distributions in the energy space, working pressure and fuel species, are also investigated. Compared with the IECF device with D–D, numerical calculations show that by increasing the percentage of tritium in the D–T mixture fuel the neutron production rate grows significantly.     

Propagation of detonation in fuel–air mixtures in flat channels

The wide scatter of the values of the measured detonation cell size in fuel + air mixtures restricts the applicability of this parameter in the estimation of the geometric limits of detonation propagation, including in rectangular channels whose height is much larger than their width. The critical channel height for the propagation of detonation has been experimentally determined for hydrogen + air, propane + air, and ethylene + air mixtures. In order to reveal the specific features of the propagation and decay of detonation in a narrow channel, numerical simulation has been carried out for a hydrogen + air mixture with account taken of the cellular structure of the detonation wave.     

Reduced methanol crossover and enhanced proton transport in nanocomposite membranes based on clay−CNTs hybrid materials for direct methanol fuel cells

Hybrid nanomaterial based on the combination between a 2D silicate structure of a smectic clay (SWy) and 1D structures of carbon nanotubes has been synthesized and used as additive in the polymer matrix of Nafion for the preparation of electrolyte nanocomposite membranes. The CNTs anchored on the clay’s lamellae were subsequently oxidized and organo-functionalized by sulphonic groups. The hybrid membranes have been tested in direct methanol fuel cells (DMFCs) and studied by NMR spectroscopy (pulse field gradient technique and relaxation times), electrochemical impedance spectroscopy and SEM microscopy. The study of the molecular dynamics of methanol and protons, as well as the tests in the DMFC, shows the effectiveness of these “branched particles” for the reduction of the methanol crossover, whilst ensuring appropriate proton conductivity, especially in conditions of low humidity and high temperature (>100 °C).     

Effect of the shape of an organic water–coal fuel particle on the condition and characteristics of its ignition in a hot air flow

The results of experimental studies of the effect of the shape of an organic water–coal fuel (OCWF) particle on its ignition delay time and the time of its complete burnout in a hot air flow are reported. Three most common shapes of real particles, such as spherical, ellipsoidal, and irregular-polyhedron-like, are considered. It is shown that the shortest ignition delay time and the time of complete burnout correspond to polyhedron- shaped OCWF particles. Conditions are identified under which this factor significantly influences the ignition characteristics. The experiments were carried out at initial particle sizes (averaged maximum values) of 0.5–5 mm and temperatures and velocities of the oxidant flow of 600–900 K and 0.5–5 m/s, respectively. The main components of the studied fuels were coal processing wastes and waste motor, turbine, and transformer oils.