氢在电镀锌层中的扩散渗透性的研究

针对氢在镀锌层中的扩散渗透性，采用电化学氢渗透技术对Ｆｅ／电镀Ｚｎ双层试样进行了研究．得到了镀锌层的厚度对镀层氢扩散系数以及氢稳态渗透通量的影响方式．研究结果表明，电镀锌层中氢扩散系数约为１０－１１ｃｍ２·ｓ－１数量级，镀锌层能够阻滞氢的扩散渗透．相应地，随镀层厚度增大，试样氢稳态渗透通量和氢有效扩散系数减小     

温度对贮氢合金MlNi3.75Co0.65Mn0.4Al0.2动力学性能的影响

在-20℃～85℃的范围内系统地研究了温度对贮氢合金MINi3.75Co0.65Mn0.4Al0.2动力学性能的影响.结果表明:该贮氢合金电极的电化学反应电阻Rt,欧姆内阻Ro,阴极极化过电位,阳极极化过电位,阳极极化过程中的电化学反应过电位ηa和浓差极化过电位ηa均随温度的升高而减小,该电极的交换电流密度i0,对称因子β和电极中氢的扩散系数D随温度的升高而增大.当放电电流密度较低时,电化学反应是整个电极过程的速度控制步骤;当放电电流密度较高时,氢的扩散是整个电极过程的速度控制步骤;在中等放电电流密度下,电极过程由电化学过程和氢的扩散过程混合控制.该电极中电化学反应过程和氢扩散过程的活化能分别为28.1 kJ·mol-1和19.9 kJ·mol-1.     

Pd/Mm(富铈稀土)薄膜电极在KOH溶液中的电化学行为

利用磁控溅射法制备了Pd/Mm(Mischmetal)混合稀土薄膜,采用X射线衍射、AFM及循环伏安和交流阻抗谱等电化学测试技术研究了Pd/Mm稀土薄膜的晶体结构、表面形貌及其在KOH溶液中的电化学行为.结果表明,Pd/Mm薄膜表面的Pd层由纳米级的孤岛状颗粒构成,颗粒大小为100～200 nm.循环伏安法研究表明,氢的电化学氧化和还原均通过表面Pd金属层进行.Pd/Mm稀土薄膜电极的交流阻抗图由两个容抗弧组成,低频区的容抗弧对应氢在电极中的固态扩散过程,而高频段的容抗弧对应氢在电极表面的电化学还原过程,其中氢在薄膜电极内部的扩散是速率控制步骤.     

温度对贮氢合金MINi~3~.~7~5Co~0~.~6~5Mn~0~.~4Al~0~.~2动力学性能的影响

在-20℃～85℃的范围内系统地研究了温度对贮氢合金MINi~3~.~7~5Co~0~.~6~5Mn~0~.~4Al~0~.~2动力学性能的影响。结果表明：该贮氢合金电极的电化学反应电阻R~t,欧姆内阻R~0,阴极极化过电位,阳极极化过电位,阳极极化过程中的电化学反应过电位η~a和浓差极化过电位η~c均随温度的升高而减小,该电极的交换电流密度i~0,对称因子β和电极中氢的扩散系数D随温度的升高而增大。当放电电流密度较低时,电化学反应是整个电极过程的速度控制步骤;当放电电流密度较高时,氢的扩散是整个电极过程的速度控制步骤;在中等放电电流密度下,电极过程由电化学过程和氢的扩散过程混合控制。该电极中电化学反应过程和氢扩散过程的活化能分别为28.1kJ.mol^-^1和19.9kJ.mol^-^1。     

电解制备二氧化锰强酸性电解液中气体扩散电极的稳定性与失效行为

采用气体扩散电极(GDE)代替传统析氢阴极电解制备二氧化锰(EMD),重点研究了气体扩散电极在强酸性MnSO4-H2SO4电解液中的稳定性、寿命及失效行为.结果表明:气体扩散电极在MnSO4-H2SO4电解液中重现性好、具有一定的稳定性,寿命可达400 h;平行实验表明,阳极沉积一定厚度的EMD是槽电压第一次升高的主要原因;电流密度为100 A m-2时,气体扩散电极失效前阴极过程的速度由氧的离子化反应和氧的扩散混合控制,失效后阴极过程由氧去极化和氢去极化共同组成,主要发生析氢反应;催化层聚四氟乙烯(PTFE)网络结构的破坏和镍网层的溶解是电极失效的原因之一;Pt的团聚降低了电极的电催化活性,是电极失效的主要原因;阴极失效是槽电压再次升高的主要原因.     

MnNi3.55Co0.75Mn0.4Al0.3合金吸氢过程动力学研究

在２２－６０℃范围内研究了贮氢合金ＭｎＮｉ３．５５Ｃｏ０．７５Ｍｎ０．４４Ａｌ０．３（Ｍｎ为富铈混合稀土金属）在ａ和α＋β相区恒温吸氢动力学过程。研究结果表明，合金在α相区吸氢受化学反应控速，动力学规律不受氢初压的影响，在整个α＋β相区吸氢过程中，受氢在合金氢物中的扩散控速，得到相应的速率方程和表观活化能。     

恒电位阶跃法研究贮氢合金MlNi_(3.75)Co_(0.65)Mn_(0.4)Al_(0.2)中氢的扩散行为

本文用恒电位阶跃法研究了不同放电深度 (DOD)和不同温度下贮氢合金MlNi3.75Co0 .6 5Mn0 .4 Al0 .2 中氢的扩散行为 .结果表明 :室温下该合金中氢的扩散系数随DOD的增大而增大 ,在5 0 %DOD的该合金中 ,氢的扩散系数随温度的升高而增大 ,扩散活化能为 19.87kJ/mol     

电化学方法测定氢在TiNi貯氢合金中的扩散系数

在20±0.3 ℃时, 用电化学方法测得氢在TiNi贮氢合金中的扩散系数为(6.45±0.78)×10~(-7)cm~2sec~(-1), 氢在这种合金中扩散过程的活化能为16.59 kJ mol~(-1)。TiNi合金电极在NaOH溶液中, 经过多次电化学渗氢以后, 在合金表面覆盖着一层钛的氧化物, 在这氧化物层的下面为富镍层。     

MmNi_（3．55）Co_（0．75）Mn_（0．4）Al_（0．3）合金吸

在２２～６０℃范围内研究了贮氢合金ＭｍＮｉ＿（３．５５）Ｃｏ（０．７５）Ｍｎ＿（０．４）Ａｌ＿（０．３）（Ｍｍ为富铈混合稀土金属）在ａ和。ａ＋β相区恒温吸氢动力学过程。研究结果表明，合金在ａ相区吸氢受化学反应控速，动力学规律不受氢初压的影响。在整个ａ＋β相区吸氢过程中，受氢在合金氢化物中的扩散控速。得到相应的速率方程和表观活化能。     

氘和氢在钯中行为的研究

自从1989年Fleischman及Pons发表了用钯阴极电解重水诱导室温核聚变(又叫“冷核聚变”)以来,多数学者对其实验结果持怀疑态度,但研究电解重水过程中氘在钯电极中的行为以及氘和氢性质之间的差异,对了解电化学诱导室温核聚变和氘及氢的贮存与利用都有重要的意义.本文用电化学渗氢技术比较了氘及氢在钯中的吸收和扩散等行为,用正电子湮没技术研究了电解前后钯中电子结构及其缺陷电子结构的变化.     

电化学阻抗法测定金属氢化物电极中氢的扩散系数

应用电化学阻抗法测定了不同荷电状态 (SOC)和不同温度下MlNi3.75Co0 .65Mn0 .4 Al0 .2 金属氢化物电极中氢的扩散系数 .结果表明 :室温下该电极中氢的扩散系数随其荷电量的增大而减小 ,SOC为 5 0 %时氢的扩散系数随温度的升高而增大 ,相应的氢扩散活化能为 35kJ/mo     

非平衡渗入条件下的电化学渗氢模型

提出非平衡渗入条件下的电化学渗氢数学模型,导出相应的渗氢电流暂态关系式。指出由稳态渗氢电流与试样厚度的关系可得表面渗入过程的动力学参数。讨论了阴极极化条件对氢扩散系数观测值的影响。     

Generation of Iron Atoms in the Gas Phase by Microwave‐Induced Plasma Afterglows

A fast‐flow reactor technique is described by which Fe atoms can be produced in the gas phase in the afterglow of microwave‐induced plasmas in hydrogen/argon and hydrogen/helium mixtures. When the iron salt FeCl₃(s) was brought into the gas phase by thermal sublimation at temperatures between 360 and 405 K, it was partly converted to Fe atoms by reaction of the gaseous compounds Fe_xCl_3x(g) with hydrogen atoms. The Fe atoms were detected by atomic absorption spectroscopy (AAS). It was shown that sublimation of the salt is the rate‐determining step of the overall plasma‐afterglow atomisation process. Experimental conditions for the generation of Fe atoms suited to kinetic studies start at a temperature of 303 K. In the downstream region the concentration of Fe atoms decays due to diffusion to the reactor wall. Binary diffusion coefficients D_Fe/Ar and D_Fe/He of 231.5±6.6 and 370.0±15.5 cm² s^?1 Torr at 303 K, respectively, were determined.     

α-Al2O3阻氢微观机制研究

采用基于密度泛函理论广义梯度近似下的平面波赝势方法研究了刚玉(α-Al2O3)的阻氢微观机制, 对氢原子在α-Al2O3中的占据结构进行了计算, 发现氢原子占据空隙位置时能量最低, 寻找其过渡态得到活化能为1.59 eV, 利用动力学计算得到了氢原子在α-Al2O3中的扩散系数表达式为D(T)=(3.37×10-7)exp(-1.59/kT). 结果表明, 氢原子占据在α-Al2O3八面体空隙处的结构最稳定; 低温时扩散难以发生; 高温时扩散沿着空隙方向.     

Effect of Thiourea on the Kinetics of the Hydrogen Evolution Reaction at Iron and the Transport of Hydrogen through a Steel Membrane in Solutions of C<Subscript>2</Subscript>H<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O-HCl

The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H₂O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum.     

Mass transport and effective diffusion coefficient in the reduction of hydrogen ions from aqueous sulfuric acid solutions: Numerical modeling

This work presents results of the numerical solution to a system of equations of material balance and the movement of particles in solution under the influence of the forces of diffusion, migration, and convection, which describe the process of mass transport during the reduction of hydrogen ions at a rotating disk electrode from aqueous sulfuric acid solutions with and without excess supporting electrolyte. Results of the calculations show that the diffusion kinetics of hydrogen ion reduction can be observed only with measurements in dilute (≤10^?3 M) sulfuric acid solutions with an excess of indifferent supporting electrolyte. For more acidic solutions it is necessary to take into account the simultaneous diffusion of hydrogen and bisulfate ions. In the study of the regularities of hydrogen ion reduction in sulfuric acid solutions with a sulfate supporting electrolyte, it is necessary to take into account that with excess supporting electrolyte, the limiting current of hydrogen reduction is caused solely by the diffusion of bisulfate ions, but for small concentration ratios of the supporting electrolyte to acid, the influence of migration effects is significant.     

Mass transfer to horizontal gas-generating electrodes

Mass transfer to a horizontal electrode during electrolytic evolution of oxygen and hydrogen at current densities of 100 to 10 000 A/m² is studied. The mass transfer intensity is evaluated from the diffusion layer thickness, which varies from 60 to 5 μm at such current densities. Calculations show that the decrease in the diffusion layer thickness is due to bubbles with a stationary interphase surface crossing the diffusion layer. During the hydrogen evolution, the diffusion layer thickness is nearly the same for vertical and horizontal electrodes. During the oxygen evolution, the diffusion layer is much thinner for a horizontal electrode. Additional decrease of the diffusion layer thickness during the evolution of oxygen is associated with the lesser solution density in the near-electrode layer and with its transport away by means of natural convection.     

MH电极中氢扩散系数的测定及其应用

利用恒流放电法测定了金属氢化物(MH)电极中氢原子扩散系数的平均值. 通过恒电位法测定了MH电极中氢原子的扩散系数与其荷电态(SOC)的关系. 根据MH电极模型可知, 增大氢原子扩散系数或减小储氢合金粒径均能提高MH电极的快速充电性能, 并能计算出MH电极在不同的初始荷电态、不同充电倍率下, 表面氢原子浓度达到最大值所需的时间.     

Nonideality in diffusion of ionic and neutral solutes and hydrogen bond dynamics in dimethyl sulfoxide-chloroform mixtures of varying composition

Molecular dynamics simulations of charged and neutral solutes in dimethyl sulfoxide (DMSO)-chloroform mixtures reveal pronounced nonideality in the solute diffusion with changes of composition of the mixtures. The diffusion coefficient of the anionic solute first decreases, passes through a minimum at DMSO mole fraction of about 0.50, and then increases to reach its value for pure DMSO. The diffusion coefficients of the cationic and neutral solutes are found to decrease with increase in DMSO content of the solvent mixture. The extent of nonideality in the diffusion and orientational relaxation of solvent molecules is found to be somewhat stronger than that in diffusion of the anionic solute in these mixtures. We have also calculated the relaxation of hydrogen bonds formed between DMSO and chloroform molecules. The lifetimes of DMSO-chloroform hydrogen bonds are found to increase monotonically with increase in DMSO concentration. The average number of hydrogen bonds and their average energies are also computed. It is found that an increase in DMSO concentration causes a decrease in the number of DMSO-chloroform hydrogen bonds per DMSO or chloroform molecules but increases the strength of these hydrogen bonds.