Investigation of stress-enhanced surface reactivity on Alloy 800 using scanning electrochemical microscopy

Scanning electrochemical microscopy (SECM) was used to simultaneously investigate the impact of tensile and compression stress on reactivity of the same Alloy 800 sample in ferrocenemethanol solution containing thiosulfate. Strong surface reactivity was observed on the stressed regions. Both tensile (the exterior edge) and compressed (inner edge) regions showed higher reactivity than the region between these. Hence both tensile stress and compression stress increased the localized surface reactivity, indicating potential for acceleration of corrosion susceptibility of Alloy 800 under stress in thiosulfate-contained chemistries.     

Recent advances of scanning electrochemical microscopy and scanning ion conductance microscopy for single-cell analysis

Single-cell analysis is important for understanding fundamental biological processes and mechanisms. Scanning electrochemical microscopy and scanning ion conductance microscopy as two kinds of scanning probe microscopy, with high temporal and spatial resolutions as well as in situ and noninvasive characterization capabilities, emerge as strong tools for single-cell analysis. In this review, we introduce the latest advances of scanning electrochemical microscopy and scanning ion conductance microscopy for single-cell analysis, including characterizations of cell morphology dynamics, membrane properties and mechanics, and monitoring cell surface charge, extracellular pH, and intracellular substances.     

In situ scanning FTIR microscopy and IR imaging of Pt electrode surface towards CO adsorption

In situ scanning FTIR microscopy was built up for the first time in the present work, which consists of an FTIR apparatus, an IR microscope, an X-Y mapping stage, and the specially designed electrochemical IR cell and computer software. It has been demonstrated that this new space-resolvd in situ IR technique can be used to study vibration properties of micro-area, and to perform IR imaging of electrode surface. The chemical image obtained using this technique fur CO adsorption on Pt electrode illustrated, at a space-resolution of 10~(-2) cm, the inhomogeneity and the distribution of reactivity of micro-area of electrode surface.     

Nanoscale surface modification via scanning electrochemical probe microscopy

Micro- and nanoscale surface modification using scanning probe microscopy techniques in combination with electrochemically induced surface structuring provides a maskless in situ fabrication strategy enabling deposition or etching of three-dimensional nanostructures. This current opinion article focuses on scanning electrochemical probe microscopy techniques highlighting recent progress in nanoscale 3D surface modification along with a spotlight on approaches of practical relevance.     

Quantification of the surface diffusion of tripodal binding motifs on graphene using scanning electrochemical microscopy

The surface diffusion of a cobalt bis-terpyridine, Co(tpy)(2)-containing tripodal compound (1·2PF(6)), designed to noncovalently adsorb to graphene through three pyrene moieties, has been studied by scanning electrochemical microscopy (SECM) on single-layer graphene (SLG). An initial boundary approach was designed in which picoliter droplets (radii ~15-50 μm) of the tripodal compound were deposited on an SLG electrode, yielding microspots in which a monolayer of the tripodal molecules is initially confined. The time evolution of the electrochemical activity of these spots was detected at the aqueous phosphate buffer/SLG interface by SECM, in both generation/collection (G/C) and feedback modes. The tripodal compound microspots exhibit differential reactivity with respect to the underlying graphene substrate in two different electrochemical processes. For example, during the oxygen reduction reaction, adsorbed 1·2PF(6) tripodal molecules generate more H(2)O(2) than the bare graphene surface. This product was detected with spatial and temporal resolution using the SECM tip. The tripodal compound also mediates the oxidation of a Fe(II) species, generated at the SECM tip, under conditions in which SLG shows slow interfacial charge transfer. In each case, SECM images, obtained at increasing times, show a gradual decrease in the electrochemical response due to radial diffusion of the adsorbed molecules outward from the microspots onto the unfunctionalized areas of the SLG surface. This response was fit to a simple surface diffusion model, which yielded excellent agreement between the two experiments for the effective diffusion coefficients: D(eff) = 1.6 (±0.9) × 10(-9) cm(2)/s and D(eff) = 1.5 (±0.6) × 10(-9) cm(2)/s for G/C and feedback modes, respectively. Control experiments ruled out alternative explanations for the observed behavior, such as deactivation of the Co(II/III) species or of the SLG, and verified that the molecules do not diffuse when confined to obstructed areas. The noncovalent nature of the surface functionalization, together with the surface reactivity and mobility of these molecules, provides a means to couple the superior electronic properties of graphene to compounds with enhanced electrochemical performance, a key step toward developing dynamic electrode surfaces for sensing, electrocatalysis, and electronic applications.     

In situ scanning FTIR microscopy and IR imaging of Pt electrode surface towards CO adsorption

In situ scanning FTIR microscopy was built up for the first time in the present work, which consists of an FTIR apparatus, an IR microscope, an X-Y mapping stage, and the specially designed electrochemical IR cell and computer software. It has been demonstrated that this new space-resolvdin situ IR technique can be used to study vibration properties of micro-area, and to perform IR imaging of electrode surface. The chemical image obtained using this technique for CO adsorption on Pt electrode illustrated, at a space-resolution of 10^-2 cm, the inhomogeneity and the distribu-tion of reactivity of micro-area of electrode surface. Project supported by the National Natural Science Foundation of China (Grant No. 29525307).     

Quantitative characterization of shear force regulation for scanning electrochemical microscopy

The quest for higher spatial resolution in scanning electrochemical microscopy (SECM) calls for the application of smaller probe electrodes. When electrodes are to be used in the feedback mode, smaller electrodes require higher intrinsic kinetics at the sample. The fabrication of nanoelectrodes, as well as their use as SECM probes at constant distance, are reported. The properties of shear force regulation system are characterized quantitatively. Simultaneous topography and reactivity imaging were demonstrated using gold microstructures on a glass substrate.     

Local desorption of thiols by scanning electrochemical microscopy: patterning and tuning the reactivity of self-assembled monolayers

Self-assembled monolayers (SAMs) are widely used in the field of nanotechnologies and (bio)sensors. The monolayer surface properties are tailored by employing several techniques. A large set of SAM post-modification routes are commonly performed to adapt them to a variety of nano-technological and bio-technological studies as well as to several bio-sensoristic applications. Here, we report a procedure to locally modify SAMs by electrochemical desorption of alkanethiols in order to create microsized spots of bare gold area without affecting the surrounding monolayer stability. The tip of the scanning electrochemical microscope (SECM) was employed to draw microstructured pattern according to a defined geometry. The time stability of the pattern was also tested. Furthermore, the patterned surface was post-functionalized using the same alkanethiol or a ferrocene-terminated thiol, in order to tune the surface reactivity of the microstructure. The local surface properties, including reactivity and electron transfer kinetics toward redox mediator reduction, were characterized by SECM.     

Fabrication of Prussian Blue modified ultramicroelectrode for GOD imaging using scanning electrochemical microscopy

A Prussian Blue (PB) film modified disk ultramicroelectrode (UME) was fabricated by electrochemical deposition technique on a Pt-disk UME. The electrocatalytical reductions of hydrogen peroxide derived from glucose oxidase (GOD) on this modified UME were investigated. The enzymatic biochemical reactivity was imaged by scanning electrochemical microscopy (SECM) utilizing the PB film modified UME. It is evident that sensitivity and spatial resolution for hydrogen peroxide measurement were improved obviously. SECM images obtained clearly revealed the concentration profile of the reaction products around the enzymes. The PB film modified microelectrode is in the nature of simple preparation, high catalytic activity on hydrogen peroxide and substrate selectivity for SECM etc.     

The local electrochemical behavior of the AA2098-T351 and surface preparation effects investigated by scanning electrochemical microscopy

In this work, scanning electrochemical microscopy (SECM) measurements were employed to characterize the electrochemical activities on polished and as-received surfaces of the 2098-T351 aluminum alloy (AA2098-T351). The effects of the near surface deformed layer (NSDL) and its removal by polishing on the electrochemical activities of the alloy surface were evaluated and compared by the use of different modes of SECM. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) were also employed to characterize the morphology of the surfaces. The surface chemistry was analyzed by X-ray photoelectron spectroscopy (XPS). The surface generation/tip collection (SG/TC) and competition modes of the SECM were used to study hydrogen gas (H₂) evolution and oxygen reduction reactions, respectively. H₂ evolution and oxygen reduction were more pronounced on the polished surfaces. The feedback mode of SECM was adopted to characterize the electrochemical activity of the polished surface that was previously corroded by immersion in a chloride-containing solution, in order to investigate the influence of the products formed on the active/passive domains. The precorroded surface and as-received surfaces revealed lower electrochemical activities compared with the polished surface showing that either the NSDL or corrosion products largely decreased the local electrochemical activities at the AA2098-T351 surfaces.     

Scanning electron microscopy in the analysis of the activity of graphite electrodes

Copper deposition patterns on graphite electrodes were analyzed by scanning electron microscopy. The deposition patterns correlate very well with the electrochemical activity of different graphites. The results indicate that treatment of graphite by electroactivation, laser irradiation of polishing on 600-grit silicon carbide paper produces active sites on the surface. The density of the sites directly reflects the electrochemical reactivity of the surface.     

Photosystem I patterning imaged by scanning electrochemical microscopy

We report the first directed adsorption of Photosystem I (PSI) on patterned surfaces containing discrete regions of methyl- and hydroxyl-terminated self-assembled monolayers (SAMs) on gold. SAM and PSI patterns are characterized by scanning electrochemical microscopy (SECM). The insulating protein complex layer blocks the electron transfer of the SECM mediator, thereby reducing the electrochemical current significantly. Uniformly and densely packed adsorbed protein layers are observed with SECM. Pattern images correlate with our previous studies where we showed that low-energy surfaces (e.g., CH3-terminated) inhibit PSI adsorption in the presence of Triton X-100, whereas high-energy surfaces (e.g., OH-terminated) enable adsorption. Therefore, a SAM pattern with alternating methyl and hydroxyl surface regions allows PSI adsorption only on the hydroxyl surface, and this is demonstrated in the resulting SECM images.     

Catalysis resolved using scanning tunnelling microscopy

The technique of scanning tunnelling microscopy has revolutionised our understanding of surface chemistry, due to its ability to image at the atomic and molecular scale, the very realm at which chemistry operates. This critical review focuses on its contribution to the resolution of various problems in heterogeneous catalysis, including surface structure, surface intermediates, active sites and spillover. In the article a number of images of surfaces are shown, many at atomic resolution, and the insights which these give into surface reactivity are invaluable. The article should be of interest to catalytic chemists, surface and materials scientists and those involved with nanotechnology/nanoscience. (129 references.)The graphical abstract shows the reaction between gas phase methanol and oxygen islands on Cu(110), courtesy of Philip Davies of Cardiff University. The added-row island is shown as silver-coloured spheres (copper) and red (oxygen) on the copper surface. Methanol preferentially reacts with the terminal oxygen atoms in the island forming adsorbed methoxy and OH groups. Only the terminal oxygen atoms in the island are active sites for the reaction.     

Novel strategy for constant-distance imaging using alternating current scanning electrochemical microscopy

Scanning electrochemical microscopy (SECM) still lacks reliable means for performing constant-distance imaging experiments. We demonstrate, for the first time, that the same negative alternating current (AC) feedback can be observed on approach to an insulator and an unbiased conductor at optimal experimental conditions. This leads to a novel constant-distance imaging mode. To perform AC-SECM imaging, only minor modifications of the existing SECM set-up were necessary. The new constant-distance AC-SECM imaging was conducted to provide topographical information not affected by variations in sample conductivity and reactivity. Furthermore, simultaneous AC and DC SECM measurements were carried out to demonstrate that both topographical and chemical information could be revealed.     

High resolution studies of heterogeneous processes with the scanning electrochemical microscope

The focus of this review is on applications of scanning electrochemical microscopy (SECM) to studies of heterogeneous chemical processes and high resolution characterization of the solid/liquid and liquid/liquid interfaces. Recent advances in SECM imaging of surface topography and chemical reactivity are also surveyed.     

Parylene insulated probes for scanning electrochemical-atomic force microscopy

Scanning electrochemical-atomic force microscopy (SECM-AFM) is a powerful technique that can be used to obtain in situ information related to electrochemical phenomena at interfaces. Fabrication of probes to perform SECM-AFM experiments remains a challenge. Herein, we describe a method for formation of microelectrodes at the tip of commercial conductive AFM probes and demonstrate application of these probes to SECM-AFM. Probes were first insulated with a thin parylene layer, followed by subsequent exposure of active electrodes at the probe tips by mechanical abrasion of the insulating layer. Characterization of probes was performed by electron microscopy and cyclic voltammetry. In situ measurement of localized electrochemical activity with parylene-coated probes was demonstrated through measurement of the diffusion of Ru(NH)(6)(3+) across a porous membrane.     

The effect of electrochemical surface treatments of carbon fibers using scanning tunneling microscopy

Scanning tunneling microscopy (STM) has been applied to the study of the topography of polyacrylonitrile (PAN)-based carbon fibers before and after electrochemical surface treatments. The results show that the electrical anodic oxidation only changes the surface aspects; at nanometric resolution; the nanostructure and nanotexture such as the step-like crystallite stacking are decreased with increasing electric current densities.     

Electrochemical concept of scanning tunnel microscopy and scanning tunnel spectroscopy

The history of investigation, development and application of electrochemical scanning tunneling microscopy (ESTM) are reviewed.     

Microcontact printed diaphorase monolayer on glass characterized by atomic force microscopy and scanning electrochemical microscopy

Micropatterns of diaphorase (Dp) were fabricated on glass substrates by the microcontact printing (μCP) method and characterized with atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM). AFM images of the printed samples revealed that the mean height of the Dp patterns was 3–5 nm, indicating the formation of a monolayer pattern. The Dp molecules on the surface organized themselves into two-dimensional arrays. We used two kinds of inking solutions: Dp–phosphate buffer solution (PBS) (pH 7.0) and Dp–PBS (pH 7.0) with glutaraldehyde (GA, 1% v/v) as a cross-linking reagent. Although the AFM imaging showed high-quality Dp monolayer patterns in both cases, SECM measurements indicated that the enzymatic activity of Dp was almost lost when Dp–PBS with GA was used as the inking solution, whereas clear enzymatic activity was found when Dp–PBS was used.     

Facilitated tip-positioning and applications of non-electrode tips in scanning electrochemical microscopy using a shear force based constant-distance mode

In scanning electrochemical microscopy (SECM) a microelectrode is usually scanned over a sample without following topographic changes (constant-height mode). Therefore, deconvolution of effects from distance variations arising from non-flat sample surface and electrochemical surface properties is in general not possible. Using a shear force-based constant distance mode, information about the morphology of a sample and its localized electrochemical activity can be obtained simultaneously. The setup of the SECM with integrated constant-distance mode and its application to non-flat or tilted surfaces, as well as samples with three-dimensional surface structures are presented and discussed. The facilitated use of non-amperometric tips in SECM like enzyme-filled glass capillaries is demonstrated.