The dynamic effect of Micro-MHD convection on bubble grown at a horizontal microelectrode

Relatively low efficiency is the biggest obstacle to the popularization of water electrolysis, which is a particularly feasible way to produce super-pure hydrogen. Imposing a magnetic field can increase the hydrogen production efficiency of water electrolysis. However, the enhancement's detailed mechanism still lacks an insightful understanding of the bubbles' micro vicinity. Our recent work aims to understand why the micro-magnetohydrodynamic (MHD) convection hinders single bubbles' detachment on the microelectrode. A water electrolysis experiment by microelectrode is performed under an electrode-normal magnetic field, and dynamic analysis of the single bubble growing on microelectrodes is performed. The variation of bubble diameter with time in the presence or absence of the magnetic field was measured, and the forces acting on the bubble were quantified. The result shows that the micro-MHD convection, induced by Lorentz force, can give rise to a downward hydrodynamic pressure force that will not appear in large-scale MHD convection. This force can be of the same magnitude as the surface tension, so it dramatically hinders bubbles' detachment. Besides, the Kelvin force provides a new potential way for further improving the efficiency of water electrolysis.     

Electrochemical micromachining using a solid electrochemical reaction at the metal/β″-Al2O3 microcontact

A simple solid state technique for electrochemical micromachining of metal substrates using a metal ion conductor (Na-β″-Al₂O₃) was proposed. The fundamental solid electrochemical cell consists of a (anode) metal substrate (M = Ag, Cu, Zn, and Pb)/pyramidal Na-β″-Al₂O₃/Ag (cathode) system, where the contact diameter between M/Na-β″-Al₂O₃ was extremely small, on the order of a few micrometer. Under an applied electric field, the metal substrate was electrochemically oxidized to metal ions (Mⁿ⁺) at the M/Na-β″-Al₂O₃ microcontact. These Mⁿ⁺ ions migrated into the Na-β″-Al₂O₃. As a result of continuous electrolysis, the metal substrate was locally consumed at the microcontact, and thus solid state electrochemical micromachining was accomplished. As expected, the machining size or depth depended on the electrolysis conditions (current, operating time) and the apex configuration of pyramidal Na-β″-Al₂O₃. Moreover, the scanning of the Na-β″-Al₂O₃ pyramid during electrolysis produced a fine patterned metal substrate. In the present paper, solid state electrochemical micromachining was performed for several metal substrates, and its advantages and disadvantages vis-a-vis the conventional electrochemical micromachining method are discussed in detail.     

Nucleation of corrosion pits in Ringer’s solution containing bovine serum

The effects of the presence of bovine serum on the nucleation of corrosion pits on 316L stainless steel and commercially pure titanium in Ringer’s physiological solution at 37 °C are presented. The experiments involved measurement of current transients generated on microelectrodes under potentiostatic control below the pitting potential. Results show that the presence of the organic components of the serum stimulates the nucleation of pits on 316L stainless steel. A similar but smaller effect is shown for commercially pure titanium.     

Passivation of pinhole defect microelectrode arrays in ultrathin silica films immobilized on gold substrates

Nanoscopic defects present in ultrathin (~ 6 nm) silica films covalently attached to gold substrates through a gold oxide layer exhibit a voltammetric response consistent with a random array of ultramicroelectrodes. These pinholes can be passivated via electrochemical polymerization of phenol to create insulating poly(phenylene) oxide plugs as documented by atomic force microscopy and infrared reflectance-absorbance spectroscopy. Passivation of pinholes is ~ 99.5% complete after 550 voltammetric cycles of oxidative electropolymerization.     

A direct analysis of nanomolar metal ions in environmental water samples with Nafion-coated microelectrodes

Square Wave Anodic Stripping Voltammetry (SWASV) was combined with microfabricated microelectrodes to analyze metal ions in aqueous solution and showed excellent performance such as short analysis time about 1 min per experiment, simultaneous detection of several ions and very low detection limit as low as several nanomoles per liter (i.e. sub-ppb in mass) without any of supporting electrolyte and stirring during analysis. Nafion, a famous ion-exchanging polymer, was introduced to protect the electrode surface from obstructing materials. The Nafion-coated microelectrode was free from disturbing impurities and was capable of analyzing natural water samples directly. Results from the direct water analysis showed similar performance to those from pre-treated samples in both sensitivity and analysis time. To secure the reproducibility of Nafion-coated electrode, a simple electrochemical cleaning method with potential sweep was used and the electrode remained reliable to continued experiments. Nafion-coated microelectrodes were further examined via the comparison with ICP-MS data.     

Carbon nanotube integrated 3-dimensional carbon microelectrode array by modified SU-8 photoresist photolithography and pyrolysis

An integration strategy is devised for a reliable and scalable assembly of carbon nanotubes in photoresist-derived glassy-like carbon microelectrodes. The approach involves UV photolithography process with carbon nanotube monodispersed photoresist followed by high temperature pyrolysis process, and is versatile in yielding various 3-dimensional micro-nano integrated carbon microelectrode arrays. The morphology of the micro-nano integrated structures is characterized. The integrated microelectrodes demonstrate better electrical performance than the blank microelectrodes, showing potential applications in high-sensitive chemical and biological detection systems. The developed method represents a low-cost and facile way to mass production of carbon nanotube-integrated carbon microelectrode array.     

La0.6Ca0.4CoO3, La0.1Ca0.9MnO3 and LaNiO3 as bifunctional oxygen electrodes

A series of perovskite catalysts was investigated for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte and at room temperature, supplied by oxygen or air. A meniscus cell was used to screen-test candidate catalysts for their bifunctionality and assess their activity for ORR at 3 mm depth of immersion (DOI) in the electrolyte. Based on the meniscus data LaNiO₃, La_0.1Ca_0.9MnO₃ and La_0.6Ca_0.4CoO₃ were selected for further assessment in microelectrode and half-cell studies. Activity tests for the ORR and OER, Tafel slopes at high current densities and apparent activation energies for the ORR were determined using a microelectrode technique on samples of the selected perovskites, La_0.1Ca_0.9MnO₃, La_0.6Ca_0.4CoO₃ and LaNiO₃ with and without graphite support. Tafel slopes of ca. 120 mV per decade and apparent activation energies of approximately 18 kcal mol⁻¹ were measured at high cathodic current densities. Cycle-life and performance of La_0.1Ca_0.9MnO₃, La_0.6Ca_0.4CoO₃ and LaNiO₃-based gas-diffusion electrodes in half-cell configurations were tested at a constant current density of 25 mA cm⁻² with subsequent and intermittent polarizations. Similar activities resulted in the ORR, while increased numbers of cycles were observed for the La_0.1Ca_0.9MnO₃-based electrode. Furthermore, electrode material compositions, especially PTFE contents were optimized to conform to the establishment of the three phase interactions of the electrode structure. Transmission Electron microscopy (TEM) and BET-surface area analyses were carried out in order to find out the morphological and surface properties of the perovskite materials.     

Crevice corrosion monitoring of titanium and its alloys using microelectrodes

Crevice corrosion of titanium and its alloys in 10% sodium chloride was investigated at 100°C with the aid of microelectrodes. Potential, pH and chloride ion concentration inside the crevice were monitored using an Ag/AgCl electrode, a tungsten microelectrode and a Ag/AgCl chloride ion selective microelectrode, respectively. The pH and Cl^? concentrations within the crevice were calculated from the standard potential‐pH and potential‐log[Cl^?] calibration curves. The effect of Mo on the crevice corrosion of titanium was also studied. The passivation behavior on the titanium and Ti‐15%Mo alloy was studied using electrochemical impedance studies. There was no apparent change in pH and Cl^? ion activity inside the crevice for the alloy at 100°C, whereas a marginal decrease in pH and increase in Cl^? ion concentration were observed for pure titanium. Thus pure titanium is susceptible to crevice corrosion in hot 10% NaCl solutions at 100°C. The chloride ion activity was found to be reduced for the alloy so that the pH inside the crevice increased. The corrosion reaction resistance (R_t) was found to increase with the addition of Mo as an alloying element. It also increases with externally applied anodic potential. Hence, Mo is an effective alloying element, which enhances the crevice corrosion resistance of titanium.     

L-Aspartic acid/L-cysteine/gold nanoparticle modified microelectrode for simultaneous detection of copper and lead

This paper presents an electrochemical microsensor for simultaneous detection of copper (II) and lead (II) using an l-aspartic acid/l-cysteine/gold nanoparticle modified microelectrode. The microelectrode was fabricated by Micro Electro-Mechanical System technique. The complex of gold nanoparticles (AuNPs) and amino acid with carboxyl group was used as the selective ligand for metal ions. The microelectrode was firstly modified with AuNPs to increase the sensitive area of the working electrode. Subsequently, the AuNPs/gold electrode was modified with l-cysteine and then covalently linked with a monolayer of l-aspartic acid using glutaraldehyde. Electrochemical analysis of metal ions was achieved by using square wave voltammetry without stirring. The microsensor exhibited an excellent linear range from 5 μg L^− 1 to 2000 μg L^− 1 with the limit of detection of 1 μg L^− 1. This metal ion detection method based on l-aspartic acid/l-cysteine/gold nanoparticle modified microelectrode is simple, sensitive and it could be used for electrochemical analysis of copper (II) and lead (II).     

神经电生理微电极阵列检测系统研制

该文设计了基于微电极阵列的16通道神经电生理信号检测系统。检测系统由硬件和软件两部分组成,其中硬件部分可分为以下3个模块:微电极阵列接口模块,用于实现微电极阵列和检测系统的可靠连接;多通道信号放大模块,用于对微弱电生理信号进行提取并放大至合适的幅度;数据采集模块,对放大后的电生理信号进行高速数据采集并通过USB2.0接口和计算机相连。软件部分采用多线程、多缓存等技术保证对信号的实时观测和分析。对检测系统的主要参数进行了测试,并结合实验室自制神经微电极阵列对SD大鼠海马区脑切片进行神经电生理信号的检测。系统的输入噪声Vrms2 V,放大倍数为1000倍,频率带宽范围为10~3000 Hz,并且能够检测到放电幅度为20 V左右的神经电生理信号。该文针对微电极阵列神经电生理信号检测中的技术难点,从硬件和软件设计上保证微弱信号的提取,检测系统的分辨率可达0.6 V,各项参数能够满足神经电生理信号的检测需要。