Rational determination of exchange current density for hydrogen electrode reactions at carbon-supported Pt catalysts

The rotating disk electrode (RDE) is a useful technique for precise determination of exchange current density (j₀) in electrochemistry. For the study of powder catalysts, a common practice is to apply the powder onto an inert disk substrate (such as glassy carbon). However, this approach in its usual version will lead to wrong results for the exchange current density of hydrogen electrode reactions at carbon-supported Pt nanoparticles (Pt/C) because of the poor utilization of the loaded Pt nanoparticles. Our new approach is to dilute the Pt/C powder with a large amount of pristine carbon support to make the catalyst layer. In this way, all the catalyst particles in the catalyst layer have nearly the same and much enhanced mass transport so that rational exchange current density can be obtained. Using the new approach, the current density for hydrogen electrode reactions at Pt/C in 0.1 M perchloric acid at 25 °C is found to be 27.2 ± 3.5 mA/cm² with an apparent activation energy 43 kJ/mol. These results are in agreement with the j₀ estimation based on real fuel cell experiments.     

Identification of electrode surface blocking by means of thin-layer cell: 1. The model

A new method for the identification of electrode surface blocking, based on the measured differences of the diffusion limiting current densities in a thin-layer cell and in a cell with rotating-disk electrode is presented. An equation describing the diffusion limiting current density dependence on the inter-electrode distance in a thin-layer cell was derived. Experimental results were obtained from measurements with model electrodes to demonstrate the possibilities for unambiguous identification of surface blocking phenomena. A model electrode, covered with a partially conductive blocking layer was also discussed and the appearance of two diffusion limiting current density levels on the voltammograms was experimentally verified.     

Rotating disk electrode analysis of oxygen reduction at platinum particles under limiting diffusion conditions

An analysis is carried out of oxygen reduction under limiting diffusion conditions on a rotating disk electrode partially covered with platinum particles (‘particulate electrode’). First a model is developed for the current response at a rotating particulate electrode, because Levich equation, used for the classical continuous disk electrodes, is not applicable in this case. The model allows for the calculation of the limiting diffusion current by an iterative algorithm, as a function of the density and size of the particles, and the constants for the adsorption/desorption and diffusion of reactants over non-covered areas of the substrate. The model is valid when there is no overlapping of surface diffusion areas around the particles. In a second part, the oxygen reduction on platinum particles electrodeposited on a glassy carbon disk is studied. Platinum particulate electrodes with a variable density and size of particles are prepared by single pulse electrodeposition technique. Limiting diffusion currents for oxygen reduction are analysed on the light of the proposed model. Values for the oxygen surface diffusivity and the equilibrium adsorption/desorption constant on the glassy carbon substrate are obtained from the analysis.     

Polarization curves in the ohmic controlled electrodeposition of metals

The conditions under which ohmic controlled metal electrodeposition occurs are discussed using a simple mathematical model. It is shown that ohmic controlled electrodeposition can be operative if the value of the exchange current density for the electrodeposition process is more than 10 times larger than the corresponding value of the limiting diffusion current density. In this case, a linear dependence of the current density on overpotential up to the value of the limiting diffusion current density can be observed. On the other hand, the initiation of dendrite growth under these circumstances is possible, even at very low values of overpotential, at the moment when the limiting diffusion current density is attained in potentiostatic electrodeposition. In this way, instead of a limiting diffusion current density plateau, an inflection point on the polarization curve can be observed, since dendritic growth is followed by an increase in the deposition current density. At the same time, it is shown that the ensemble of tips of dendrites can behave as an ensemble of microelectrodes working independently under mixed or activation control due to the absence of a common diffusion layer. This was confirmed by deposition of copper on a copper dendritic electrode and by silver electrodeposition from a silver nitrate solution onto a graphite substrate.     

Influence of an electrochemically generated gas phase on pressure drop in a three-dimensional electrode and an inert bed

The influence of an electrochemically generated gas phase on the pressure drop in a three-dimensional electrode and an inert bed has been investigated. The electrode was composed of silvered glass particles, whereas the inert bed was composed of glass particles of the same diameter. During water electrolysis smaller gas bubbles are generated than by introducing gas into the system by means of a fluid distributor. Electrochemically generated bubbles with the liquid phase circulate upward through the electrode and the inert bed. The pressure drop for a monophase fluid was measured, as well as the change of pressure drop with time in the electrode and the inert bed for two-phase flow of fluid through an electrochemical cell. The steady and unsteady periods of the change of pressure drop have been discussed. Experiments were carried out at different electrolyte velocities and for different current densities. Higher electrolyte velocities cause an increase in the pressure drop in both beds. Also, increased current density causes an increase in gas evolution intensity at the electrode thereby increasing the pressure drop in both beds. A mathematical model describing the change of pressure drop with time has been proposed. The proposed model showed good agreement with experimental results as well as the results from the literature.     

Mass transfer in fluidized beds of inert particles. Part I: The role of collision currents in mass transfer to the electrode

The effect of particle-wall collision on the mass transfer rate mechanism in liquid fluidized bed electrochemical cells was studied. Collision frequencies and currents were measured at microelectrodes set in the bed wall. It is postulated that, at each particle–electrode collision, a specific microvolume of bulk concentration electrolyte is introduced into the near-electrode diffusion layer during particle movement towards the electrode causing an enhancement of the limiting diffusion current. Based on measurements made at microelectrodes calculations of the contribution of the particle collision mechanism to total mass transfer to a planar electrode are attempted and are in good agreement with experimental values.     

Application of conventional activated carbon loaded with dispersed Pt to PEFC catalyst layer

Improvement of the polymer electrolyte fuel cell (PEFC) requires development of highly active electrodes of low cost to facilitate its widespread use. In the present study, the possibility of applying conventional activated carbon particles loaded with Pt to the electrode catalyst layer was tested because the particles were promising in dispersion of Pt and preparation cost. The catalyst layer was formed from the particles and Nafion® and was supported as a thin film on a rotating glassy carbon disk electrode (GC RDE). Activity for oxygen reduction was evaluated by the hydrodynamic voltammetry in perchloric acid to give a current free of the influence of mass transfer in the solution. Compared with a conventional catalyst layer formed from carbon black loaded with Pt, the new catalyst layer exhibited a significant, approximately 6-fold increase in current in the high potential region corresponding to a 100 mV increase in electrode potential. Activity, however, was retarded in the low potential region. This disadvantage was overcome by mixing a conductive agent into the layer and covering it with another layer containing carbon black loaded with Pt. This double catalyst layer exhibited increased activity across all potential regions, indicating the availability of the activated carbon in the electrodes.     

采用常规条形流场的质子交换膜燃料电池阴极数值模拟(Ⅱ)电池性能影响因素的分析

利用已建立的数学模型考察了阴极扩散特性参数、阴极流场几何参数、电极电阻、催化剂活性、流道上O₂浓度变化对H₂-Air PEMFCs性能的影响.计算表明,增大氧有效扩散系数、减小扩散层厚度可增大电池的工作电流密度;提高氧还原反应交换电流密度、减小电极电阻、优化流道尺寸可改善电池性能;沿反应气体流动方向逐渐增加MEA的催化剂负载量可提高电流密度分布的均匀性.     

Structure investigations of SOFC anode cermets Part I: Porosity investigations

The number of electrolyte/metal/pore three-phase boundaries in the SOFC anode cermet was determined in a cross-section photo according to the intercepted-segment method and given as the volume concentration of the electrochemically active phase boundary. The apparent geometrical exchange current density of hydrogen oxidation served as a relativizing measure of electrochemical activity. A direct correlation was found between the number of optically visible three-phase boundaries of electrolyte/nickel agglomerates/gas pores' in the unit volume of the electrode and the apparent electrochemical exchange current density. The electrode was also analysed porosimetrically by a standard porosimetry method (MSP) and the porosimetric curves were compared with the optical/electrochemical measurements of the same electrode. This comparison revealed that the sum of the integrated volume of nickel agglomerates and the single nickel particles in contact with the electrolyte give the total amount of the active nickel volume whose surface is directly proportional to the amount of optically visible three-phase boundaries in the unit volume.     

顺丁烯二酸在锡电极上的动力学参数研究

采用稳态极化法和不同温度下稳态极化曲线法研究了酸性介质中顺丁烯二酸在锡电极上阴极还原的动力学过程,计算了相关的动力学参数,结果表明：顺丁烯二酸在锡电极上的交换电流密度i0为0．0024A／cm2,传递系数仅为0．288,表观活化能为19．266kJ／mol,低于顺丁烯二酸在铅电极上电还原反应的表观活化能,证明顺丁烯二酸在锡电极上更容易被还原。     

Rotating nanoparticle array electrode for the kinetic study of reactions under mixed control

A method for the determination of the intrinsic electrocatalytic activity of metal nanoparticles for reactions under mixed diffusion-activation control is proposed. The working electrode consists of a nanoparticle array supported on a rotating disc of an inert conducting substrate. This electrode configuration reduces significantly the contribution of the reactant diffusion to the experimental current-potential curves and consequently, the kinetic parameters of the reaction can be evaluated more accurately. A model was developed for the diffusion process in the proposed configuration, which includes a parameter related to the degree of dispersion of the nanoparticles on the electrode surface (active area factor). It allows one to evaluate changes in the current-potential plot under conditions of constant particle diameter, which is essential for the appropriate analysis of the electrocatalytic activity of nanoparticles. On this basis the dependences of the current and current density for the hydrogen oxidation reaction on overpotential, rotation rate, particle size and active area factor were derived. The validity of these expressions was verified through the analysis of experimental results.     

惰性粒子对流化结晶过程动力学特性的影响

通过惰性粒子对氯化钾流化结晶过程成核速率、晶体生长速率及晶型影响的实验研究，揭示了外加惰性粒子对流化床结晶动力学特性的影响机理和规律,并回归建立了相关数学模型。实验结果表明，惰性粒子主要通过与晶体的碰撞产生大量二次晶核，进而对晶体生长速率产生负面影响，并改变了晶型。其主要影响因素为惰性粒子的密度和尺寸。     

Optimization of the dispersion of gold and platinum nanoparticles on indium tin oxide for the electrocatalytic oxidation of cysteine and arsenite

Gold and platinum nanoparticles (NPs) were prepared by chemical reduction of the corresponding metal complex bound by ion-exchange to generation-4 poly(amidoamine) dendrimers (PAMAM). Arrays of the NPs on indium tin oxide (ITO) electrodes were formed by adsorbing a monolayer comprising a controlled ratio of NP-PAMAM to PAMAM on ITO that was modified with 3-aminopropyl triethoxysilane; subsequently, the organic components were thermally destroyed. Varying the above-defined ratio resulted in a commensurate change of the density of the NPs on the surface. Using an electrode modified in a solution with a mole fraction of Au-PAMAM (relative to total of Au-PAMAM and PAMAM) of 0.06, which gave NPs separated by 200 nm, the current for the catalytic oxidation of cysteine reached a value that did not increase when more nanoparticles were present. The analogous experiment on the oxidation of As^III with PtNPs as the catalyst was optimized at a mole fraction of 0.2. Calculations assuming hemispherical diffusion suggested that the diffusion domains during cyclic voltammetry at 5 mV s⁻¹ were less than the distance between the NPs.     

惰性粒子对气液固三相流化结晶粒度分布的影响

引　言换热壁面垢层的形成增加了热阻和流动阻力 ,降低了换热效率 ,严重时可产生局部过热损坏整个换热设备 ,使得设备的维护、检修费用增加 .李修伦、张利斌等[1,2 ] 80年代以来开发出的三相流化床蒸发沸腾换热技术较好地解决了这一问题 ,然而将该技术应用于带有结晶过程的体系 (如卤水蒸发器 )时 ,由于引入的惰性粒子对结晶过程来说为一外来杂质 ,会对晶体的生长产生影响[3] ,而早期的试验也出现过晶粒变小的问题[4 ] .因此有必要对此进行研究 ,为进一步完善和改进三相流化床技术的工业应用提供必要的基础 .1　实验研究1.1　实验装置及流程…     

A novel approach for computing tertiary current distributions based on simplifying assumptions

A novel yet efficient method for the computation of simplified tertiary current density and surface concentration distributions in electrochemical processes is presented. The method is rooted in the important physiochemical property that the activation potential is constant and uniform for given electrode material during the electrolysis. The technique is attractive because it involves a single iterative procedure against the conventional doubly iterative procedure. The initial assumption of current distribution along the electrode is also not necessary, as it involves only an assumption of a suitable power series to solve steady state laminar convective diffusion. Accordingly the method is relevant only for electrodes of constant activation polarization, but this holds good for situations where the electrode configurations are such that the primary current density distribution is almost uniform and for situations where the Wagner number is high. To illustrate the utility of the technique the procedure is applied to some realistic problems encountered in electrochemical engineering such as the current distribution either in plane-parallel plate electrode with electrolyte flowing between them or a moving electrode with the electrolyte stationary.     

Platinum Nanoclusters Exhibit Enhanced Catalytic Activity for Methane Dehydrogenation

Methane utilization, whether by steam reforming or selective oxidation to produce synthesis gas or alcohols, requires the activation and dissociation of at least one carbon?Chydrogen bond. At high temperatures, using platinum nanoparticles as catalysts, this process operates with low activity. However, the catalyst particle shape may be controlled at low temperatures, and faceted particles may catalyze hydrocarbon transformation with increased activity. In this study, we use density functional theory calculations to calculate the thermodynamics of methane dehydrogenation on both (hemi)spherical and tetrahedral platinum nanoclusters. We show all steps of methane dehydrogenation on the hemispherical cluster have high activation barriers (0.4?C1.0?eV), thus requiring high temperatures for this process. However, the energy barriers for methane dehydrogenation on the tetrahedral cluster are lower than the corresponding barriers on the hemispherical cluster, and in particular, the dissociation of the methyl group to form methylene and hydrogen has an activation barrier of only 0.2?eV. Thus, we expect that hydrogen production from methane would proceed at a higher rate and conversion on tetrahedral clusters than on hemispherical clusters. The resulting hydrogen and carbon-containing species may then serve as building blocks for the production of chemicals and fuels. We believe that catalyst shape is vitally important in controlling catalytic activity, and the use of faceted catalyst particles opens up possibilities for low-temperature and energy-efficient hydrocarbon transformations.     

PEM fuel cell reaction kinetics in the temperature range of 23-120 °C

The performance of a Nafion 112 based proton exchange membrane (PEM) fuel cell was tested at a temperature range from 23 °C to 120 °C. The fuel cell polarization curves were divided into two different ranges based on current density, namely, <0.4 A/cm² and >0.4 A/cm², respectively. These two ranges were treated separately with respect to electrode kinetics and mass transfer. In the high current density range, a linear increase in membrane electrode assembly (MEA) power density with increasing temperature was observed, indicating the advantages of high temperature operation.Simulation based on electrode reaction kinetic theory, experimental polarization curves, and measured cathodic apparent exchange current densities all gave temperature dependent apparent exchange current densities. Both the calculated partial pressures of O₂ and H₂ gas in the feed streams and the measured electrochemical Pt surface areas (EPSAs) decrease with increasing temperature. They were also used to obtain the intrinsic exchange current densities. A monotonic increase of the intrinsic exchange current densities with increasing temperature in the range of 23-120 °C was observed, suggesting that increasing the temperature does promote intrinsic kinetics of fuel cell reactions.There are two sets of cathode apparent exchange current densities obtained, one set is for the low current density range, and the other is for the high current density range. The different values of cathode current densities in the two current density ranges can be attributed to the different states of the cathode Pt catalyst surface. In the low current density range, the cathode catalyst surface is a Pt/PtO, and in the high current density range, the catalyst surface becomes pure Pt.     

喷动床研究与进展

叙述了近年来出现的几种改型喷动床，包括多喷头喷动床、喷动流化床、带导向管的喷动床、性粒子旋转射流式喷动床、射流喷动床的研究与进展。它们在传统柱锥形喷动床的基础上，通过增加喷口、导向管、流化气、惰性粒子或增加喷动气速等方法，来克服原有喷动床应用的局限性，拓展其应用领域。     

基于阴离子交换反应的NiMn-LDH电极电容性能提升研究

采用一步水热法在泡沫镍网上原位生长镍锰基层状双氢氧化物（NiMn-LDH）纳米片阵列电极,并通过氢氧化钾溶液中浸泡的方式提升电极的容量。采用SEM、XRD、TEM和XPS等手段对浸泡前后的电极材料进行表征。结果表明,在浸泡前后NiMn-LDH电极的形貌没有变化,但在电极材料内部发生了明显的CO₃^2-和OH^-的交换反应,降低体积较大的CO₃^2-在LDH层间的分布数量,使层内空间成为OH^-的“蓄水池”,缩短了电荷存储过程中OH^-的迁移距离,因此电容性能有了明显提升。电化学测试结果表明,在5 mA/cm²电流密度下,电极的比电容从18.0 F/g增加至766.6 F/g（1.69 F/cm²）。将该电极与活性炭组装的全固态不对称超级电容器在功率密度为900 W/kg时,可呈现的能量密度为35.9 W·h/kg,并且器件的循环稳定性良好。