Electorchemical Studies of Cytochrome c on Electodes Modified by Single—Wall Carbon Naotubes

Single-wall carbon nanotubes(SWNTs) modified gold electrodes were prepared by using two different methods.The electrochemical behavior of cytochrome c on the modified gold electrodes was investigated.The first kind of SWNT-modified electrode (noted as SWNT/Au electrode)was prepared by the adsorption of carboxylterminated SWNTs from DMF dispersion on the gold electrode.The oxidatively processed SWNT tips were covalently modified by coupling with amines (AET) to form amide linkage.Via Au-S chemical bonding,the self-assembled monolayer of thiol-unctionalized nanotubes on gold surface was fabricated so as to prepare the others SWNT-modified electrode (noted as SWNT/AET/Au electrode).It was shown from cyclic voltammetry cxperiments that cytochrome c exhibited direct electrochemical responses on the both electrodes, but only the current of controlled diffusion existed on the SWNT/Au electrode while both the currents of controlled diffusion and adsorption of cytochrome c occurred on the SWNT/AET/Au electrode.Photoelastic Modulation Infared Reflection Absorpthion Spectroscopy (PEM-IRRAS) and Quartz Crystal Microbalance (QCM) were employed to verify the adsorption of SWNTs on the gold electrodes.The results proved that SWNTs could enhance the direct electron transfer proecss between the electrodes and redox proteins.     

Analytical applications of Raman spectroscopy

In this article interaction of transition metal complexes with DNA and its applications in electrochemical DNA biosensors as hybridization indicator or electroactive marker of DNA are reviewed. Special emphasis has been given to the efforts for the development of new transition metal complexes and their interaction to DNA. DNA and polymers covalently conjugated with transition metal complexes were also reviewed.     

Comparison of two accelerated Nafion™ degradation experiments

This work describes a systematic investigation of the degradation of Nafion™ 112 membranes using a Fenton's accelerated aging experiment. Two variations of the experiment were compared: a solution method where iron ions and peroxide exist together in solution prior to the addition of Nafion™, and an exchange method where Nafion™ in the Fe²⁺ form is exposed to hydrogen peroxide. Accelerated aging experiments were conducted over 3-5 days. Weight loss, fluoride ion release, ion exchange capacity, intrinsic viscosity, morphological characteristics, and dimensional changes were measured. FTIR spectra, mechanical properties and membrane barrier properties were also investigated.     

The chemical behavior and degradation mitigation effect of cerium oxide nanoparticles in perfluorosulfonic acid polymer electrolyte membranes

Perfluorosulfonic acid membranes are susceptible to degradation during hydrogen fuel cell operation due to radical attack on the polymer chains. Mitigation of this attack by cerium-based radical scavengers is an approach that has shown promise. In this work, two formulations of crystalline cerium oxide nanoparticles, with an order of magnitude difference in particle size, are incorporated into said membranes and subjected to proton conductivity measurements and ex-situ durability tests. We found that ceria is reduced to Ce(III) ions in the acidic environment of a heated, humidified membrane which negatively impacts proton conductivity. In liquid and gas Fenton testing, fluoride emission is reduced by an order of magnitude, drastically increasing membrane longevity. Sideproduct analysis demonstrated that in the liquid Fenton test, the main point of attack is weak polymer end groups, while in the gas Fenton test, there is additional side-chain attack. Both mechanisms are mitigated by the addition of the ceria nanoparticles, whereby the extent of the concentration-dependent durability improvement is found to be independent of particle size.     

一种新型的用于质子交换膜燃料电池的磺化聚醚醚酮酮

以发烟硫酸和4,4-二(4-氟苯甲酰基)苯[1,4-bi(4-fluorobenzoyl)benzene]为原料,通过磺化反应,制得磺化二氟三苯二酮[1,4-bi(3-sodiumsulfonate-4-fluorobenzoyl)benzene].利用亲核缩聚反应,调整磺化单体和非磺化单体的比例,与酚酞进行聚合,制取了具有不同磺化度的聚醚醚酮酮,并对聚合物的结构进行了表征.结果表明,此系列磺化聚醚醚酮酮的膜制品具有良好的离子交换特性,可望应用于燃料电池膜.     

PEMFC插指型流道阴极中气体扩散特性的数值分析

本文对PEMFC插指型流道阴极扩散层建立了二维单相的多组分物理数学模型,对PEMFC插指型流道的阴极扩散层中气体的扩散特性及反应行为进行了数值研究,采用有限容积法对模型控制方程进行求解,比较了插指型和平直型流道两类电池的性能曲线,以及两种流道中氧气的组分摩尔浓度和局部电流密度的分布,分析了插指型流道结构参数对电池性能的影响。     

Existence of weak positive solutions to a nonlinear PDE system around a triple phase boundary, coupling domain and boundary variables

We consider a 2D nonlinear system of PDEs representing a simplified model of processes near a triple-phase boundary (TPB) in cathode catalyst layer of hydrogen fuel cells. The particularity of this system is the coupling of a variable satisfying a PDE in the interior of the domain with another variable satisfying a differential equation (DE) defined only on the boundary, through an adsorption-desorption equilibrium mechanism. The system includes also an isolated singular boundary condition which models the flux continuity at the contact of the TPB with a subdomain. By freezing certain terms we transform the nonlinear PDE system to an equation, which has a variational formulation. We prove several L^∞ and W1,p a priori estimates and then by using Schauder fixed point theorem we prove the existence of a weak positive bounded solution.     

Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt-based Electrocatalysts – Part I: High-loading Pt/C and Pt Extended Surface

Kinetic isotope effect (KIE) was used to study the rate-determining step for oxygen reduction reaction (ORR) on dispersed Pt/C electrocatalyst and polycrystalline Pt (Pt-poly). KIE is defined as the ratio of the kinetic current measured in protonated electrolyte versus deuterated electrolyte, with KIE values larger than one indicating proton participation in the rate-determining step. The effect of poisoning anions on the platinum rate determining step is investigated by assessing the KIE in perchloric (non-poisoning) and sulfuric acid-based electrolytes. The kinetics currents were calculated using the Koutechy-Levich and Tafel analysis. A KIE of 1 was observed for Pt/C (with a 40 wt.% Pt loading) and Pt-poly, thus indicating that, on 40 wt. % Pt/C and Pt-poly, the rate determining step is proton independent.     

随机振动问题的广义坐标合成法

工程中的随机振动分析多采用完全二次型组合法(CQC)及其改进算法,如虚拟激励法(PEM)和谐波激励法(HEM)。广义坐标合成法(GCS)提出了一种计算随机响应的新思路,其基本原理是将物理空间的计算转移到自由度较小的振型空间进行,从而缩减了计算量和计算规模。对于较大规模结构体系的随机振动问题,GCS方法计算响应协方差矩阵的计算量只相当于PEM的2r/sT,其中s、r和T分别为激励功率谱矩阵的秩、振型总数和离散频率点数。此外,对于给定激励时程的问题,由于GCS方法直接求解广义坐标运动方程,因而可以方便得出响应时程。通过对几种方法的详细对比,说明对于大多数只需要求解响应方差的随机振动问题,GCS是最优的计算方法。PEM只有在sPEM。