Fabrication of Scanning Electrochemical Microscopy-Atomic Force Microscopy Probes to Image Surface Topography and Reactivity at the Nanoscale.

Concurrent mapping of chemical reactivity and morphology of heterogeneous electrocatalysts at the nanoscale allows identification of active areas (protrusions, flat film surface, or cracks) responsible for productive chemistry in these materials. Scanning electrochemical microscopy (SECM) can map surface characteristics, record catalyst activity, and identify chemical products at solid-liquid electrochemical interfaces. It lacks, however, the ability to distinguish topographic features where surface reactivity occurs. Here, we report the design and fabrication of scanning probe tips that combine SECM with atomic force microscopy (AFM) to perform measurements at the nanoscale. Our probes are fabricated by integrating nanoelectrodes with quartz tuning forks (QTFs). Using a calibration standard fabricated in our lab to test our probes, we obtain simultaneous topographic and electrochemical reactivity maps with a lateral resolution of 150 nm.

Seeing through Walls at the Nanoscale: Microwave Microscopy of Enclosed Objects and Processes in Liquids.

Noninvasive in situ nanoscale imaging in liquid environments is a current imperative in the analysis of delicate biomedical objects and electrochemical processes at reactive liquid-solid interfaces. Microwaves of a few gigahertz frequencies offer photons with energies of ≈10 µeV, which can affect neither electronic states nor chemical bonds in condensed matter. Here, we describe an implementation of scanning near-field microwave microscopy for imaging in liquids using ultrathin molecular impermeable membranes separating scanning probes from samples enclosed in environmental cells. We imaged a model electroplating reaction as well as individual live cells. Through a side-by-side comparison of the microwave imaging with scanning electron microscopy, we demonstrate the advantage of microwaves for artifact-free imaging.

High-contrast and fast electrochromic switching enabled by plasmonics.

With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light--propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer--present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer.

Optical Fluorescence Microscopy for Spatially Characterizing Electron Transfer across a Solid-Liquid Interface on Heterogeneous Electrodes.

Heterogeneous catalytic materials and electrodes are used for (electro)chemical transformations, including those important for energy storage and utilization.1, 2 Due to the heterogeneous nature of these materials, activity measurements with sufficient spatial resolution are needed to obtain structure/activity correlations across the different surface features (exposed facets, step edges, lattice defects, grain boundaries, etc.). These measurements will help lead to an understanding of the underlying reaction mechanisms and enable engineering of more active materials. Because (electro)catalytic surfaces restructure with changing environments,1 it is important to perform measurements in operando. Sub-diffraction fluorescence microscopy is well suited for these requirements because it can operate in solution with resolution down to a few nm. We have applied sub-diffraction fluorescence microscopy to a thin cell containing an electrocatalyst and a solution containing the redox sensitive dye p-aminophenyl fluorescein to characterize reaction at the solid-liquid interface. Our chosen dye switches between a nonfluorescent reduced state and a one-electron oxidized bright state, a process that occurs at the electrode surface. This scheme is used to investigate the activity differences on the surface of polycrystalline Pt, in particular to differentiate reactivity at grain faces and grain boundaries. Ultimately, this method will be extended to study other dye systems and electrode materials.

Atomic force microscopy of electrochemical nanoelectrodes.

Nanometer-sized electrodes have recently been used to investigate important chemical and biological systems on the nanoscale. Although nanoelectrodes offer a number of advantages over macroscopic electrochemical probes, visualization of their surfaces remains challenging. Thus, the interpretation of the electrochemical response relies on assumptions about the electrode shape and size prior to the experiment and the changes induced by surface reactions (e.g., electrodeposition). In this paper, we present first AFM images of nanoelectrodes, which provide detailed and unambiguous information about the electrode geometry. The effects of polishing and cleaning nanoelectrodes are investigated, and AFM results are compared to those obtained by voltammetry and SEM. In situ AFM is potentially useful for monitoring surface reactions at nanoelectrodes.

Nanoelectrodes for determination of reactive oxygen and nitrogen species inside murine macrophages.

Reactive oxygen and nitrogen species (ROS and RNS) produced by macrophages are essential for protecting a human body against bacteria and viruses. Micrometer-sized electrodes coated with Pt black have previously been used for selective and sensitive detection of ROS and RNS in biological systems. To determine ROS and RNS inside macrophages, one needs smaller (i.e., nanometer-sized) sensors. In this article, the methodologies have been extended to the fabrication and characterization of Pt/Pt black nanoelectrodes. Electrodes with the metal surface flush with glass insulator, most suitable for quantitative voltammetric experiments, were fabricated by electrodeposition of Pt black inside an etched nanocavity under the atomic force microscope control. Despite a nanometer-scale radius, the true surface area of Pt electrodes was sufficiently large to yield stable and reproducible responses to ROS and RNS in vitro. The prepared nanoprobes were used to penetrate cells and detect ROS and RNS inside macrophages. Weak and very short leaks of ROS/RNS from the vacuoles into the cytoplasm were detected, which a macrophage is equipped to clean within a couple of seconds, while higher intensity oxidative bursts due to the emptying of vacuoles outside persist on the time scale of tens of seconds.

Scanning electrochemical microscopy in the 21st century. Update 1: Five years after.

This Perspective is an update to our more extensive survey of scanning electrochemical microscopy (SECM) published in 2007. During this time, the SECM field retained its momentum by expanding into new areas and meeting the emerging scientific and technological challenges. Here we focus on most prominent developments such as high-resolution imaging, investigation of structures and processes on the nanoscale, alternative energy applications, and new approaches to solving "real world" problems. The fabrication of novel SECM probes and related theoretical advances are also discussed.

Polished nanopipets: new probes for high-resolution scanning electrochemical microscopy.

Nanometer-sized pipets pulled from glass or quartz capillaries have been extensively used as probes for scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM). A small separation distance between such a probe and the sample, which is required for high-resolution SECM measurements, may be hard to attain because of considerable roughness of the pipet tip. In this Letter, we report the preparation and characterization of polished nanopipet SECM probes with a much smoother tip edge. Using polished pipets, quantitative SECM measurements were performed at extremely short tip/substrate distances (e.g., d ≈ 1 nm).

Fabrication of nanoelectrodes and metal clusters by electrodeposition.

Most nanometer-sized electrodes reported to date are made from either Pt or Au. For technical reasons, it is difficult to make nanoelectrodes from many other metals (e.g. Hg) by heat-sealing microwires into glass capillaries or by other established techniques. Such nanoelectrodes can be useful for a wide range of analytical and physicochemical applications from high sensitivity stripping analysis (Hg) to pH nano-sensors to studies of electrocatalysis. In this paper, nanometer-sized metal electrodes are prepared by electrodeposition of Hg or Pt on disk-type, polished or recessed nanoelectrodes. The deposition of Hg is monitored chronoamperometrically to produce near-hemispherical electrodes, which are characterized by voltammetry and scanning electrochemical microscopy (SECM). The well-shaped deposits of a solid metal (Pt) at Au nanoelectrodes are prepared and imaged by scanning electron microscopy (SEM). Catalytic metal clusters can also be prepared using this methodology. Electrodes with the metal surface flush with glass insulator, most suitable for quantitative voltammetric and SECM experiments are fabricated by electrodeposition of a metal inside an etched nanocavity.

Electrochemistry through glass.

In this Article we have used new approaches to investigate a well-known chemical process, the propagation of electrochemical signals through a thin glass membrane. This process, which has been extensively studied over the last century, is the basis of the response of a potentiometric glass pH sensor; however, no amperometric glass sensors have yet been reported because of its high ohmic resistance. Voltammetry at nanoelectrodes has revealed that water molecules can diffuse through nanometre-thick layers of dry glass and undergo oxidation/reduction at the buried platinum surface. After soaking for a few hours in an aqueous solution, voltammetric waves of other redox couples, such as Ru(NH(3))(6)(3+/2+), could also be obtained at the glass-covered platinum nanoelectrodes. This behaviour suggests that the nanometre-thick insulating glass sheath surrounding the platinum core can be largely converted to hydrated gel, and electrochemical processes occur at the platinum/hydrogel interface. Potential applications range from use in nanometre-sized solid-state pH probes and determination of the water content in organic solvents to glass-modified voltammetric sensors and electrocatalysts.

Kinetic study of rapid transfer of tetraethylammonium at the 1,2-dichloroethane/water interface by nanopipet voltammetry of common ions.

Steady-state voltammetry at the pipet-supported liquid/liquid interface has previously been used to measure kinetics of simple and facilitated ion transfer (IT) processes. Recently, we showed that the conventional experimental protocol and data analysis produce large uncertainties in kinetic parameters of rapid IT processes extracted from pipet voltammograms. Here, we used a new mode of nanopipet voltammetry, in which a transferable ion is initially present as a common ion in both liquid phases, and improved methodology for silanization of the outer pipet wall to investigate the kinetics of the rapid transfer of tetraethylammonium (TEA(+)) at the 1,2-dichloroethane/water interface. This reaction was often employed as a model system to check the IT theory. The determined standard rate constant and transfer coefficient of the TEA(+) transfer are compared with previously reported values to demonstrate limitations of conventional nanopipet voltammetry with a transferrable ion present only in one liquid phase.

Adsorption/desorption of hydrogen on Pt nanoelectrodes: evidence of surface diffusion and spillover.

Nanoelectrochemical approaches were used to investigate adsorption/desorption of hydrogen on Pt electrodes. These processes, which have been extensively studied over the last century, remain of current interest because of their applications in energy storage systems. The effective surface area of a nanoelectrode was found to be much larger than its geometric surface area due to surface diffusion of adsorbed redox species at the Pt/glass interface. An additional peak of hydrogen desorption was observed and attributed to the spillover of hydrogen from the Pt surface into glass. The results were compared to those obtained for underpotential deposition of copper on Pt nanoelectrodes.

Nanoscale imaging of surface topography and reactivity with the scanning electrochemical microscope.

Over the last 2 decades, scanning electrochemical microscopy (SECM) has been extensively employed for topographic imaging and mapping surface reactivity on the micrometer scale. We used flat, polished nanoelectrodes as SECM tips to carry out feedback mode imaging of various substrates with nanoscale resolution. Constant-height and constant-current images of plastic and Au compact disc surfaces and more complicated objects (computer chips and wafers) were obtained. The possibility of simultaneous imaging of surface topography and electrochemical reactivity was demonstrated. Very fast mass transfer at nanoelectrodes allowed us to obtain high-quality electrochemical images in viscous media under steady-state conditions, e.g., in 1-methyl-3-octylimidazolium-bis(tetrafluoromethylsulfonyl)imide (C(8)mimC(1)C(1)N) ionic liquid. Ion-transfer-based imaging was also performed using nanopipets as SECM tips.