SECM基本原理及其在金属腐蚀中的应用

扫描电化学显微镜（SECM）是一种具有较高空间分辨率的化学显微镜,在成像和动力学研究已经广泛应用. 本文简要介绍SECM基本原理,综述2009年以来SECM在腐蚀方面的应用,包括扫描成像和异相转移电子化学活性的研究,并简要介绍了作者课题组在SECM方面的研究工作,展望SECM在腐蚀研究的应用.     

SECM Studies on the Electrocatalytic Oxidation of Glycerol at Copper Electrodes in Alkaline Medium

This study aims at analyzing the reaction mechanism of the electrooxidation of glycerol at copper surfaces in NaOH solutions using Scanning Electrochemical Microscopy (SECM) in the substrate generation/tip collection (SG/TC) mode. Experiments showed the dependence of the current at the tip on the distance between generator and tip, as well as on the concentration of the NaOH solution. The current at the tip decreased significantly after addition of glycerol, as a result of the competition between diffusion of the free‐soluble Cu(III) species and its consumption during the diffusion in the solution. The determination of the analyte in a castor biodiesel sample employing a single copper microelectrode was carried out.     

SECM imaging of MMD-enhanced latent fingermarks

Scanning electrochemical microscopy (SECM) has been used to image latent fingermarks enhanced by adsorption of gold nanoparticles onto which silver is chemically deposited, a process known as "multi-metal-deposition" (MMD).     

Proton transport in radiation-grafted membranes for fuel cells as detected by SECM

Scanning electrochemical microscopy (SECM) has been applied to investigate counter ion transport through four different proton conducting membranes with poly(styrene sulfonic acid) side chains. These membranes, intended for the polymer electrolyte fuel cell, are based on PVDF and PVDF-co-HFP matrix materials and have been prepared by an irradiation grafting method. SECM is found to be suitable for mapping variations in proton diffusion coefficient and concentration in these inhomogeneous membranes. It was found that the variations in these parameters are most considerable in a membrane with a high degree of grafting. Ionic conductivities measured with impedance spectroscopy were in agreement with calculated values obtained on the basis of the SECM measurements.     

Investigation of ion-bombarded conducting polymer films by scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) was used to investigate the effect of ion bombardment on thin films of the conducting polymers poly[3-ethoxy-thiophene] (PEOT) and poly[ethylenedioxy-thiophene] (PEDT). Bombardment with Ar+-ions converts the topmost 30 nm thick layer to an essentially insulating material. SECM approach curves as well as two dimensional scans prove the existence of regions of different conductivity within the irradiated regions that did not show a significant dependence on ion dosage. PEDT layers patterned by ion bombardment through microscopic masks are investigated as prototypes of miniaturized printed circuit boards that can be formed by galvanic copper deposition onto conducting PEDT. Defects in conducting polymer patterns were analyzed by SECM imaging before any deposition of copper. Appropriate representations of SECM images for the evaluation of this technologically important question are discussed.     

SECM for Studying the Immobilization and Repartition of a Redox Anti-tetracycline Aptamer on Screen-printed Carbon Electrodes

Scanning electrochemical microscopy (SECM) is discussed as a versatile tool to provide a unique approach of localized electrochemical information in the context of biosensing research. The step-by-step immobilization of DNA aptamer with intrinsic redox activity on screen-printed carbon electrode (SPCE) was successfully monitored using SECM imaging tool. Control experiments were performed with a non-electroactive aptamer. After immobilization of these aptamers, SECM images showed the repartition of the electroactive anti-tetracycline aptamer when comparing with images produced for control and for all modification steps of SPCE. The possibility of tetracycline detection was also proved by causing a decrease in recorded current.     

Investigation of ion-bombarded conducting polymer films by scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) was used to investigate the effect of ion bombardment on thin films of the conducting polymers poly[3-ethoxy-thiophene] (PEOT) and poly[ethylenedioxy-thiophene] (PEDT). Bombardment with Ar⁺-ions converts the topmost 30 nm thick layer to an essentially insulating material. SECM approach curves as well as two dimensional scans prove the existence of regions of different conductivity within the irradiated regions that did not show a significant dependence on ion dosage. PEDT layers patterned by ion bombardment through microscopic masks are investigated as prototypes of miniaturized printed circuit boards that can be formed by galvanic copper deposition onto conducting PEDT. Defects in conducting polymer patterns were analyzed by SECM imaging before any deposition of copper. Appropriate representations of SECM images for the evaluation of this technologically important question are discussed.     

In situ scanning electrochemical microscopy (SECM) detection of metal dissolution during zinc corrosion by means of mercury sphere-cap microelectrode tips

This work presents a scanning electrochemical microscopy (SECM)-based in situ corrosion probing methodology that is capable of monitoring the release of zinc species in corrosion processes. It is based on the use of Hg-coated Pt microelectrodes as SECM tips, which offer a wider negative potential range than bare platinum or other noble-metal tips. This allows for the reduction of zinc ions at the tip to be investigated with low interference from hydrogen evolution and oxygen reduction from aqueous solutions. The processes involved in the corrosion of zinc during its immersion in chloride-containing solutions were successfully monitored by scanning the SECM tip, set at an adequate potential, across the sample either in one direction or in the X-Y plane parallel to its surface. In this way, it was possible to detect the anodic and cathodic sites at which the dissolution of zinc and the reduction of oxygen occurred, respectively. Additionally, cyclic voltammetry (CV) or constant potential measurements were used to monitor the release of zinc species collected at the tip during an SECM scan.     

扫描电化学显微镜在电催化氧反应研究中的应用

本综述首先简单介绍了扫描电化学显微镜的基本概况,尤其是不同的工作模式. 其次,有针对性地介绍了SECM的不同工作模式在氧还原和水解析氧反应相关研究中的应用. 最后,对扫描电化学显微镜未来在新能源转换存储系统研究领域的应用进行了展望.     

The effect of electric field on potentiometric Scanning Electrochemical Microscopic imaging

Potentiometric Scanning Electrochemical Microscopy (SECM) is a powerful tool in corrosion science. It allows the selective imaging of a particular ionic species released at the anodic sites in a corrosion microcell, by using ion-selective microelectrodes (ISMEs) as scanning probes. Galvanic corrosion is a particularly often studied process. The measured potential of the ISME is thought to depend only on the activity of the primary ion. However, an electric field is also formed as a result of the potential difference between the surfaces of the galvanic pair, which has a direct influence on the potential of the sensing microelectrode; the measured potential is the sum of these two contributions. The potential difference caused by the electric field can be substantially large, exceeding that of the potential difference associated with the activity of the primary ion. In this paper, we present experimental evidence of this feature, and investigate the extent to which it influences the final chemically-resolved image.     

Analytical Expressions for Quantitative Scanning Electrochemical Microscopy (SECM)

Scanning electrochemical microscopy (SECM), is a recent analytical technique in electrochemistry, which was developed in the 1990s and uses microelectrodes to probe various surfaces. Even with the well‐known disc microelectrodes, the system geometry is not as simple as in regular electrochemistry. As a consequence even the simplest experiments, the so‐called positive and negative feedback approach curves, cannot be described with exact analytical expressions. This review gathers all the analytical expressions available in the SECM literature in steady‐state feedback experiments. Some of them are claimed as general expressions, other are presented as approximate. Their validity is discussed in the light of the current understanding and computer facilities.     

有机涂层／金属界面腐蚀的微区电化学

以扫描开尔文探针，局部交流阻抗和扫描电化学显微镜为代表的微区电化学技术以其高精度、高空间解析度的定域分析优势被广泛应用。本文简要介绍了这三种技术的测量原理和关键问题，并着重归纳了这些技术应用于有机涂层／金属界面腐蚀行为的研究成果，包括界面微区表观形貌的获取，不同界面腐蚀机制的推理验证及其影响因素的作用机理等，并对三种技...     

Scanning electrochemical microscopy (SECM) of nanolitre droplets using an integrated working/reference electrode assembly

Scanning electrochemical microscopy (SECM) has been performed in the restricted space of nanolitre droplets with a robust and easy-to-handle coaxial electrode assembly centring a Pt microdisk in a circular Ag electrode. Straightforward and reproducible fabrication of the specially designed probe tips was achieved by using Tollens reaction to chemically deposit a uniform and well-adhering layer of silver on the body of a glass-insulated Pt microdisk electrode. The suitability of the novel dual-electrode SECM tip for measurement in small volumes was evaluated by imaging an array of four Pt band microelectrodes in 500 nL electrolyte.     

Visualization of the Local Catalytic Activity of Electrodeposited Pt–Ag Catalysts for Oxygen Reduction by means of SECM

Pt–Ag nanoparticle co‐deposits with different Pt–Ag ratios were prepared on a glassy carbon (GC) surface by pulsed electrodeposition and investigated for their catalytic activity in electrocatalytic oxygen reduction by using cyclic voltammetry (CV), rotating disc electrode (RDE) and scanning electrochemical microscopy (SECM) in 0.1 M phosphate buffer (pH 7.0). The atomic composition of the Pt–Ag co‐deposits was studied by means of energy‐dispersive X‐ray analysis (EDAX). In combination with X‐ray diffraction (XRD), the presence of partly alloyed Pt and Ag on the GC surface was confirmed. Scanning electron microscopy (SEM) images indicate that the prepared Pt–Ag catalyst particles are homogenously dispersed over the GC surface. Their size and morphology depend on their composition. The electrocatalytic activity of Pt–Ag deposits with high Pt content was the highest, exceeding even that of electrodeposited Pt as evaluated by quantitative RDE analysis. The redox competition mode of scanning electrochemical microscopy (RC‐SECM) was successfully used to visualize the local catalytic activity of the deposited Pt–Ag particles. Semi‐quantitative assessment of the SECM results confirmed the same order of activity of the different catalysts as the RDE investigations.     

A combined redox-competition and negative-feedback SECM study of self-healing anticorrosive coatings

In this paper, the long-term anticorrosive efficiency of a damaged self-healing coating is studied for the first time using scanning electrochemical microscopy (SECM). In the study an epoxy-coating with embedded-capsules containing a silyl-ester is employed. The properties of the silyl-ester as a healing-agent for the protection of AA2024-T3 were evaluated by complementary SECM experiments operating in negative-feedback and redox-competition modes. The experimental approach here presented allowed for monitoring the early-stages of corrosion activity and subsequent healing mechanisms offered by the release of silyl-ester into a relatively large coating defect. This result was observed by detecting the transition of the oxygen reduction response from a redox-competition mode to a negative-feedback behavior. These measurements demonstrated that the silyl-ester is released efficiently after capsules break upon coating damage, covering relatively large areas and gradually healing the damaged-site hindering the corrosion processes and providing an effective protection for at least one month of immersion in chloride solution.     

SECM study of the pH distribution over Cu samples treated with 2-mercaptobenzothiazole in NaCl solution

This paper reports the effect of treatment with 2-mercaptobenzothiazole (2MBT) (a corrosion inhibitor) on pH distribution over Cu samples monitored in situ using scanning electrochemical microscopy (SECM) in potentiometric mode. Line scans were conducted over two copper wires embedded in insulating resin, one of which had been pre-treated with 2MBT. It was found that the treated Cu sample had a less acidic character than the non-treated sample. Furthermore, the pH above the resin areas is considerably more acidic than that above either Cu wire. This feature is attributed to the consumption of OH⁻ ions on the non-treated Cu wire during the formation of atacamite as a corrosion product, and the tautomeric equilibrium established by the detached 2-mercaptobenzothiazole molecules in the bulk electrolyte. These pH distributions are spatially resolved in the SECM mapping above both Cu wires.     

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth‐ and Bismuth/Lead Alloy Film‐Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 mol L^?1 NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi³⁺ and Pb²⁺ ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury‐coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5 % RSD) were obtained.     

Determination of Paracetamol in Presence of Ascorbic Acid in Pharmaceutical Products by Scanning Electrochemical Microscopy

The selective amperometric determination of paracetamol in pharmaceutical formulations containing ascorbate was achieved by removing the interfering species in the diffusion layer created between a platinum substrate and a disc microelectrode in a Scanning Electrochemical Microscopy (SECM) configuration, while the target analyte was kept unconsumed. After complete depletion of ascorbate, paracetamol was detected at the SECM tip in a free‐interference solution zone. The influence of the substrate potential and the gap distance on the efficiency of ascorbate removal was systematically examined. The effectiveness of the device towards the determination of paracetamol in pharmaceutical samples was evaluated and under optimal conditions the results obtained agreed well with the labeled value.     

Stressed Corrosion of an Austenitic Stainless Steel Studied by Scanning Kelvin Probe Force Microscopy

Under the ambient temperature (25°C) and pressure (one Standard Atmospheric Pressure) conditions, surface Volta potential of an austenitic stainless steel was measured using the Scanning Kelvin Probe Force Microscopy (SKPFM) to study its stressed-related corrosion behavior in a 0.5 M chloride solution. In an oxygen and water regulated environment (using a glovebox), the steel shows a map of Volta potentials with high contrasts among the different grains and grain boundaries, which was then linked to the actual corrosion potential (w.r.t. a saturated calomel electrode) based on a rigorous calibration procedure. Corrosion behavior of the steel under tensile stress was then compared to that of the same sample under no tensile stress in light of the measured Volta potential, which was found to be sensitive to the level of applied tensile stress, although the tested stainless steel in general is known for its high corrosion-resident capability. According to this study, surface Volta potential measured by SKPFM can be used as a high-accuracy indicator for localized corrosion of steels.     

Effect of Residual Stress on Corrosion Sensitivity of Carbon Steel Studied by SECM

The effect of compressive residual stress on the reactivity of carbon steel in a neutral chloride solution was investigated by means of potentiodynamic polarization and local electrochemical measurement with scanning electrochemical microscope（SECM）. Meanwhile, X-ray diffraction, as a nondestructive technique, was employed to determine the levels of residual stress in near-surface layers of carbon steel specimen. The results show that the resi- dual stress existed in the specimen fell into the category of compressive residual stress which was inversely propor- tional to the corrosion sensitivity of carbon steel specimen. By using I/I3 couple as a redox mediator in the current feedback mode of SECM measurements, the Faradaic current on Pt tip, which was relevant to the rate of the I3- ion reduction, fell with the increase of compressive residual stress. The correlation between compressive residual stress and heterogeneous electron transfer rate has been proposed based on the inference of the localized electrochemical reactions occurred on the specimen surface,