Novel Hybrid Electrocatalyst with Enhanced Performance in Alkaline Media: Hollow Au/Pd Core/Shell Nanostructures with a Raspberry Surface

In this paper, a hollow Au/Pd core/shell nanostructure with a raspberry surface was developed for methanol, ethanol, and formic acid oxidation in alkaline media. The results showed that it possessed better electrocatalyst performance than hollow Au nanospheres or Pd nanoparticles. The nanostructure was fabricated via a two-step method. Hollow Au nanospheres were first synthesized by a galvanic replacement reaction, and then they were coated with a layer of Pd grains. Several characterizations such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS) were used to investigate the prepared nanostructures.

Extending electrochemical activity of polyaniline to alkaline media via electrostatic interaction and sol-gel route

The electroactivity of polyaniline was extended to pH = 14 alkaline media by preparation of a novel electrostatic interaction conductive hybrid from water-borne conductive polyaniline and silica network containing carboxyl groups via sol-gel process. In addition, the obtained conductive polyaniline hybrid film displayed very low conductivity threshold percolation and demonstrated excellent stability upon cycling.

Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media

Ordered hexagonal mesoporous silica material (JLU-30) has been successfully synthesized in alkaline media at high temperature (> 160 degreesC, using cationic (1,3-dimethyl-2-imidazolidin-2-ylidene)hexadecylmethyl-ammonium bromide (DIHAB) as a template, and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, differential thermal analysis (DTA), and thermogravimetric analysis (TG), as well as Al-27 and Si-29 nuclear magnetic resonance (NMR) spectroscopy. Mesoporous JLU-30 shows much higher hydrothermal stability than MCM-41. Si-29 NMR spectra indicate that the pore walls of JLU-30 samples synthesized at high temperature (160 degreesC) are fully condensed, giving a Q(4)/Q(3) ratio as high as 6.2. In contrast, MCM-41 synthesized at relatively low temperature (100 degreesC) shows the Q(4)/Q(3) + Q(2) ratio at 1.1. Such unique structural feature might be responsible for the observed highly hydrothermal stability of the mesoporous silica materials (JLU-30).

Nanoelectrocatalyst based on high-density Au/Pt hybrid nanoparticles supported on a silica nanosphere

A high-efficiency nanoelectrocatalyst based on high-density Au/Pt hybrid nanoparticles supported on a silica nanosphere (Au-Pt/SiO2) has been prepared by a facile wet chemical method. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy are employed to characterize the obtained Au-Pt/SiO2. It was found that each hybrid nanosphere is composed of high-density small Au/Pt hybrid nanoparticles with rough surfaces. These small Au/Pt hybrid nanoparticles interconnect and form a porous nanostructure, which provides highly accessible activity sites, as required for high electrocatalytic activity. We suggest that the particular morphology of the AuPt/SiO2 may be the reason for the high catalytic activity. Thus, this hybrid nanomaterial may find a potential application in fuel cells.

Electrostatic interaction hybrids from water-borne conductive polyaniline and inorganic precursor containing carboxyl group

Electrostatic interaction conductive hybrids were prepared in water/ethanol solution by the sol-gel process from inorganic sol containing carboxyl group and water-borne conductive polyaniline (cPANI). The electrostatic interaction hybrids film displayed 1-2 orders of magnitude higher electrical conductivity in comparison with common hybrids film, showing remarkable conductivity stability against water soaking. Most strikingly, it displayed ideal electrochemical activity even in a solution with pH = 14, which enlarged the conducting polyaniline application window to strong alkaline media.

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of camphorsulfonic acid

Polyaniline-camphorsulfonic acid (PAN-CSA) composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of camphorsulfonic acid (CSA). It was found that the doping of polyaniline (PAN) with CSA extends the electroactivity of PAN in neutral and even in alkaline media. The PAN-CSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anodic peak potential of AA shifts from 0.63 V at the bare platinum electrode to 0.34 V at the PAN-CSA composite modified platinum electrode with a greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-50 mM using cyclic voltammetry. The kinetics of the catalytic reaction are investigated using rotating disk electrode voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-CSA composite on the electrode surface shows good reproducibility and stability.

Preparation of highly dispersed gold microparticles and their electrocatalytic activity for the oxidation of formaldehyde

The electrochemical preparation of highly dispersed Au microparticles on the surfaces of glassy carbon (GC) electrodes and their electrocatalytic activities for the oxidation of formaldehyde were studied. It was found that the reduction of Au3+ to Au is controlled by diffusion and the formation mechanism of Au microparticles on the GC surfaces corresponds to an instantaneous nucleation and diffusion-controlled three dimensional growth process. The particle size is about 80-90 nm in diameter after the electrochemical ageing treatment. These highly dispersed Au microparticles have high surface areas and exhibit better electrocatalytic activity than that of bulk-form Au toward the electrochemical oxidation of formaldehyde in alkaline media.

Preparation and characterization of cationic corn starch with a high degree of substitution in dioxane-THF-water media

Cationic corn starch derivatives with a high degree of substitution are prepared in alkaline solution or in mixed media of organic solvent and water with different levels of the cationic reagent, 2,3-epoxypropyltrimethylammonium chloride. The starch cationization yield is investigated, and the results indicate that the degree of substitution (DS) of the samples depends on the reaction conditions and reaction media. The maximum DS values are up to 1.37 in 1,4-dioxane alkali ne-aqueous solution. Meanwhile, the structures of the cationic starch derivatives are characterized by elemental analyses, FTIR spectroscopy, X-ray diffraction, and C-13 NMR spectroscopy, as well as by SEM techniques.

Parameters Inversion of Fluid-Saturated Porous Media Based on Neural Networks

The multi-layers feedforward neural network is used for inversion of material constants of fluid-saturated porous media. The direct analysis of fluid-saturated porous media is carried out with the boundary element method. The dynamic displacement responses obtained from direct analysis for prescribed material parameters constitute the sample sets training neural network. By virtue of the effective L-M training algorithm and the Tikhonov regularization method as well as the GCV method for an appropriate selection of regularization parameter, the inverse mapping from dynamic displacement responses to material constants is performed. Numerical examples demonstrate the validity of the neural network method.

Kramers Escape Rate in Nonlinear Diffusive Media

In this paper, we study nonlinear Kramers problem by investigating overdamped systems ruled by the one-dimensional nonlinear Fokker-Planck equation. We obtain an analytic expression for the Kramers escape rate under quasistationary conditions by employing

State Vector: A New Approach to Prediction of the Failure of Brittle Heterogeneous Media and Large Earthquakes

The concept of state vector stems from statistical physics, where it is usually used to describe activity patterns of a physical field in its manner of coarsegrain. In this paper, we propose an approach by which the state vector was applied to describe quantitatively the damage evolution of the brittle heterogeneous systems, and some interesting results are presented, i.e., prior to the macro-fracture of rock specimens and occurrence of a strong earthquake, evolutions of the four relevant scalars time series derived from the state vectors changed anomalously. As retrospective studies, some prominent large earthquakes occurred in the Chinese Mainland (e.g., the M 7.4 Haicheng earthquake on February 4, 1975, and the M 7.8 Tangshan earthquake on July 28, 1976, etc) were investigated. Results show considerable promise that the time-dependent state vectors could serve as a kind of precursor to predict earthquakes.

Catastrophic Rupture Induced Damage Coalescence in Heterogeneous Brittle Media

In heterogeneous brittle media, the evolution of damage is strongly influenced by the multiscale coupling effect. To better understand this effect, we perform a detailed investigation of the damage evolution, with particular attention focused on the catastrophe transition. We use an adaptive multiscale finite-element model (MFEM) to simulate the damage evolution and the catastrophic failure of heterogeneous brittle media. Both plane stress and plane strain cases are investigated for a heterogeneous medium whose initial shear strength follows the Weibull distribution. Damage is induced through the application of the Coulomb failure criterion to each element, and the element mesh is refined where the failure criterion is met. We found that as damage accumulates, there is a stronger and stronger nonlinear increase in stress and the stress redistribution distance. The coupling of the dynamic stress redistribution and the heterogeneity at different scales result in an inverse cascade of damage cluster size, which represents rapid coalescence of damage at the catastrophe transition.

Long-Range Stress Redistribution Resulting From Damage in Heterogeneous Media

It has been shown in CA simulations and data analysis of earthquakes that declustered or characteristic large earthquakes may occur with long-range stress redistribution. In order to understand long-range stress redistribution, we propose a linear-elastic but heterogeneous-brittle model. The stress redistribution in the heterogeneous-brittle medium implies a longer-range interaction than that in an elastic medium. Therefore, it is surmised that the longer-range stress redistribution resulting from damage in heterogeneous media may be a plausible mechanism governing main shocks.

Adaptive Mesh Refinement FEM for Damage Evolution of Heterogeneous Brittle Media

Damage evolution of heterogeneous brittle media involves a wide range of length scales. The coupling between these length scales underlies the mechanism of damage evolution and rupture. However, few of previous numerical algorithms consider the effects of the trans-scale coupling effectively. In this paper, an adaptive mesh refinement FEM algorithm is developed to simulate this trans-scale coupling. The adaptive serendipity element is implemented in this algorithm, and several special discontinuous base functions are created to avoid the incompatible displacement between the elements. Both the benchmark and a typical numerical example under quasi-static loading are given to justify the effectiveness of this model. The numerical results reproduce a series of characteristics of damage and rupture in heterogeneous brittle media.