Recent high-bandwidth recordings of the oxidation and dissolution of 35 nm radius Ag nanoparticles at a Au microelectrode show that these nanoparticles undergo multiple collisions with the electrode, generating multiple electrochemical current peaks. In the time interval between observed current peaks, the nanoparticles diffuse in the solution near the electrolyte/electrode interface. Here, we demonstrate that simulations of random nanoparticle motion, coupled with electrochemical kinetic parameters, quantitatively reproduce the experimentally observed multicurrent peak behavior. Simulations of particle diffusion are based on the nanoparticle-mass-based thermal nanoparticle velocity and the Einstein diffusion relations, while the electron-transfer rate is informed by the literature exchange current density for the Ag/Ag+ redox system. Simulations indicate that tens to thousands of particle–electrode collisions, each lasting ∼6 ns or less (currently unobservable on accessible experimental time scales), contribute to each experimentally observed current peak. The simulation provides a means to estimate the instantaneous current density during a collision (∼500–1000 A/cm2), from which we estimate a rate constant between ∼5 and 10 cm/s for the electron transfer between Ag nanoparticles and the Au electrode. This extracted rate constant is approximately equal to the thermal collisional velocity of the Ag nanoparticle (4.6 cm/s), the latter defining the theoretical upper limit of the electron-transfer rate constant. Our results suggest that only ∼1% of the surface atoms on the Ag nanoparticles are oxidized per instantaneous collision. The combined simulated and experimental results underscore the roles of Brownian motion and collision frequency in the interpretation of heterogeneous electron-transfer reactions involving nanoparticles.

Here we report the direct observation and quantitative analysis of single redox events on a modified indium–tin oxide (ITO) electrode. The key in the observation of single redox events are the use of a fluorogenic redox species and the nanoconfinement and hindered redox diffusion inside 3-nm-diameter silica nanochannels. A simple electrochemical process was used to grow an ultrathin silica film (∼100 nm) consisting of highly ordered parallel nanochannels exposing the electrode surface from the bottom. The electrode-supported 3-nm-diameter nanochannels temporally trap fluorescent resorufin molecules resulting in hindered molecular diffusion in the vicinity of the electrode surface. Adsorption, desorption, and heterogeneous redox events of individual resorufin molecules can be studied using total-internal reflection fluorescence (TIRF). The rate constants of adsorption and desorption processes of resorufin were characterized from single-molecule analysis to be (1.73 ± 0.08) × 10–4 cm·s–1 and 15.71 ± 0.76 s–1, respectively. The redox events of resorufin to the non-fluorescent dihydroresorufin were investigated by analyzing the change in surface population of single resorufin molecules with applied potential. The scan-rate-dependent molecular counting results (single-molecule fluorescence voltammetry) indicated a surface-controlled electrochemical kinetics of the resorufin reduction on the modified ITO electrode. This study demonstrates the great potential of mesoporous silica as a useful modification scheme for studying single redox events on a variety of transparent substrates such as ITO electrodes and gold or carbon film coated glass electrodes. The ability to electrochemically grow and transfer mesoporous silica films onto other substrates makes them an attractive material for future studies in spatial heterogeneity of electrocatalytic surfaces.

In this Technical Note, we describe a method to fabricate nanopore-supported Pt nanoparticle electrodes and their use in bipolar electrochemistry. A Pt nanoparticle is deposited on the orifice of a solid-state nanopore inside a focused-ion beam (FIB) system. Complete blockage of the nanopore with Pt metal forms a closed bipolar nanoparticle electrode whose size and shape can be tunable in one simple step. Nanoparticle electrodes and their arrays can be prepared on different substrates such as the tip of a glass pipet, a double-barrel pipet, and a freestanding silicon nitride membrane. Steady-state voltammetry can be performed on such nanoparticle electrodes via bipolar electrochemistry. Moreover, an array of Pt nanoparticles can be used for fluorescence-enabled electrochemical microscopy. Future use of highly advanced FIB systems may allow nanoparticles of <10 nm to be fabricated which may enable coupled electrochemical reactions of single redox molecules. Pipette-supported single particle electrodes may also find useful applications in high resolution imaging with nanoscale scanning electrochemical microscopy (SECM) and neurochemical analysis inside single cells.

Electrostatic interactions play an essential role in many analytical applications including molecular sensing and transport studies using nanopores and separation of charged species. Here, we report the voltammetric quantification of electrostatic ion enrichment in a 5–20 nm thin electrochemical cell. A simple lithographic micro/nanofabrication process was used to create ultrathin-layer cells (UTLCs) with a critical dimension (i.e., cell thickness) as small as 5 nm. The voltammetric response of a UTLC was found to be largely dominated by the electrostatic interaction between charges on the cell walls and the redox species. We show that the ultrasmall cell dimension yielded a 100–300-fold enrichment for cationic redox species. An interesting surface adsorption effect was also demonstrated.

Metal nanoparticles are key electrode materials in a variety of electrochemical applications including basic electron-transfer study, electrochemical sensing, and electrochemical surface enhanced Raman spectroscopy (SERS). Metal nanoparticles have also been extensively applied to electrocatalytic processes in recent years due to their high catalytic activity and large surface areas. Because the catalytic activity of metal nanoparticle is often highly dependent on their size, shape, surface ligands, and so forth, methods for examining and better understanding the correlation between particle structure and function are of great utility in the development of more efficient catalytic systems. Despite considerable progress in this field, the understanding of the structure–activity relationships remains challenging in nanoparticle-based electrochemistry and electrocatalysis due to limitations associated with traditional ensemble measurements. One of the major issues is the ensemble averaging of the electrocatalytic response which occurs over a very large number of nanoparticles of various sizes and shapes. Additionally, the electrochemical response can also be greatly affected by properties of the ensemble itself, such as the particle spacing.The ability to directly measure kinetics of electrochemical reactions at structurally well-characterized single nanoparticles opens up new possibilities in many important areas including nanoscale electrochemistry, electrochemical sensing, and nanoparticle electrocatalysis. When a macroscopic electrode is placed in a solution containing redox molecules and metal nanoparticles, random collision and adsorption of nanoparticles occurs at the electrode surface in addition to redox reactions when a suitable potential is present on the electrode. In a special case where particles are catalytically more active than the substrate, the faradaic signals can be greatly amplified on particle surfaces and a steady shift in the baseline current would be expected due to many particles adsorbing on the electrode.Single particle events can be temporally resolved when an ultramicroelectrode (UME) is used as the recording electrode. The use of an UME not only reduces the collision frequency, but also greatly decreases baseline noise, thereby resulting in clear resolution of single collision events. Single particle collision has quickly grown into a popular electroanalytical technique in recent years. Alternatively, one can use nanoelectrodes to immobilize single nanoparticles so that they can be individually studied in electrochemistry and electrocatalysis. Nanoparticle immobilization also allows one to obtain detailed structural information on the same particles and offers enormous potential for developing more comprehensive understanding of the structure–function relationship in nanoparticle-based electrocatalysts. This Account summarizes recent electrochemical experiments of single metal nanoparticles which have been performed by our group using both of these schemes.

The dynamic collision behavior of the electro-oxidation of single Ag nanoparticles is observed at Au microelectrodes using stochastic single-nanoparticle collision amperometry. Results show that an Ag nanoparticle collision/oxidation event typically consists of a series of 1 to ∼10 discrete “sub-events” over an ∼20 ms interval. Results also show that the Ag nanoparticles typically undergo only partial oxidation prior to diffusing away from the Au electrode into the bulk solution. Both behaviors are characterized and shown to exist under a variety of experimental conditions. These previously unreported behaviors suggest that nanoparticle collision and electro-dissolution is a highly dynamic process driven by fast particle–electrode interactions and nanoparticle diffusion.

Here, we report a nanopipette-based electrochemical approach to prepare metal nanoelectrodes with excellent control over electrode size, shape, and thickness of the insulation wall. Nanoelectrodes are prepared by electrochemical plating in a laser-pulled quartz nanopipette tip immersed in a liquid gallium/indium alloy electrode, which not only protects the ultrasmall quartz tip but also starts electrodeposition from the tip orifice. This versatile approach enables reproducible fabrication of electrodes of several different metals, including gold, platinum, silver, and copper. Moreover, nanoelectrodes with varying sizes can be easily prepared by focused ion-beam milling. A unique aspect of this method is the control over the thickness of quartz insulation walls relative to the size of the electroactive surface enabling control of the RG (defined as the radius of the insulating sheath over the radius of the active metal electrode). As such, these nanoelectrodes may be especially attractive as useful nanoprobes in high-resolution imaging applications, such as scanning electrochemical microscopy.

We report direct observation of electrochemical and thermal dealloying processes of individual metal alloy nanoparticles (NPs). Electrochemical dealloying of single Ag–Hg alloy NPs was achieved in a basic solution (e.g., pH 13) by oxidizing Hg under controlled potentials. Ag can also be oxidized during single-particle collision. However, it requires elevated potentials. The strong basic environment promoted the formation of metal oxides during collision leading to a unique core–shell type nanostructure which was further confirmed by transmission electron microscopy (TEM). In thermal dealloying, Hg was evaporated due to the use of a high-energy electron beam and the process was imaged in situ inside a TEM. Both electrochemical and thermal dealloying processes resulted in the transformation of an amorphous NP to a more stable Ag–Hg alloy nanocrystal. This work demonstrates that NP collision can be a useful tool to study dealloying processes of various nanomaterials at a single-particle level.

Here we report the use of Fast-Scan Cyclic Voltammetry (FSCV) to study transient nanoparticle (NP) collision experiments and determine the apparent heterogeneous electron-transfer (ET) rate constant ko and electrocatalytic activity of single NPs. Continuous potential scanning at fast scan rates, for example, up to 500 V/s, and background subtraction enable voltammetric study of single NPs when they collide on a carbon ultramicroelectrode (UME). The FSCV results indicate a substantial potential shift in the CV response of single NPs due to increased mass transfer and it is necessary to consider this effect when analyzing single NP electrocatalysts. FSCV results also reveal that single particle deactivation is associated with a decrease in peak current and an increase in overpotential. Importantly, the use of FSCV coupled with numerical simulations enabled the determination of ko on single NPs, confirming an increase in catalytic activity with decreasing particle size. Moreover, the Gibbs free energy of activation can be estimated from the ko. This work further confirms that FSCV is a powerful method in studying dynamic electrochemical processes such as single NP collisions.

Here we report the preparation, characterization, and electrochemical study of conductive, ultrathin films of cross-linked metal nanoparticles (NPs). Nanoporous films ranging from 40 to 200 nm in thickness composed of gold and platinum NPs of ∼5 nm were fabricated via a powerful layer-by-layer spin coating process. This process allows preparation of uniform NP films as large as 2 × 2 cm2 with precise control over thickness, structure, and electrochemical and electrocatalytic properties. Gold, platinum, and bimetallic NP films were fabricated and characterized using cyclic voltammetry, scanning electron microscopy, and conductance measurements. Their electrocatalytic activity toward the oxygen reduction reaction (ORR) was investigated. Our results show that the electrochemical activity of such NP films is initially hindered by the presence of dense thiolate cross-linking ligands. Both electrochemical cycling and oxygen plasma cleaning are effective means in restoring their electrochemical activity. Gold NP films have higher electric conductivity than platinum possibly due to more uniform film structure and closer particle–particle distance. The electrochemical and electrocatalytic performance of platinum NP films can be greatly enhanced by the incorporation of gold NPs. This work focuses on electrochemical characterization of cross-linked NP films and demonstrates several unique properties. These include quick and easy preparation, ultrathin and uniform film thickness, tunable structure and composition, and transferability to many other substrates.

Fabrication plays a key role in determining the unique electrical, optical, and catalytic properties of metal nanowires. Here we present a bipolar electrochemical method for dynamically monitoring and controlling the rate of single metal nanowire growth in situ without a direct electrical connection. Solutions of a metal precursor and a reducing agent are placed on either side of a silica nanochannel, and a pair of electrodes is used to apply a tunable electric potential across the channel. Metal nanowire growth is initiated by chemical reduction when the two solutions meet and continues until the nanochannel is blocked by the formation of a short metal wire segment. Further growth is driven by a bipolar electrochemical mechanism which enables the reduction of metal precursor ions at one end of the nanowire and the oxidation of the reducing agent at the other. The growth rate is monitored in real time by simultaneously recording both the faradaic current and optical microscope video and can be adjusted accordingly by changing the applied electric potential. The resulting nanowire is solid, electrically insulated, and can be used as a bipolar nanoelectrode. This technique can be extended to other electrochemical systems, as well, and provides a confined reaction space for studying the dynamics of any process that can be optically or electrically monitored.Keywords: bipolar electrochemistry; controlled fabrication; gold; metal deposition; nanochannel; nanoelectrode; nanowire;

Here we report the use of fast-scan cyclic voltammetry (FSCV) to study transient collision and immobilization events of single electrocatalytic metal nanoparticles (NPs) on an inert electrode. In this study, a fast, repetitive voltage signal is continuously scanned on an ultramicroelectrode and its faradaic signal is recorded. Electrocatalytically active metal NPs are allowed to collide and immobilize on the electrode resulting in the direct recording of the transient voltammetric response of single NPs. This approach enables one to obtain the transient voltammetric response and electrocatalytic effects of single catalytic NPs as they interact with an inert electrode. The use of FSCV has enabled us to obtain chemical information, which is otherwise difficult to study with previous amperometric methods.

Recently, we introduced a new electrochemical imaging technique called fluorescence-enabled electrochemical microscopy (FFEM). The central idea of FEEM is that a closed bipolar electrode is utilized to electrically couple a redox reaction of interest to a complementary fluorogenic reaction converting an electrochemical signal into a fluorescent signal. This simple strategy enables one to use fluorescence microscopy to observe conventional electrochemical processes on very large electrochemical arrays. The initial demonstration of FEEM focused on the use of a specific fluorogenic indicator, resazurin, which is reduced to generate highly fluorescent resorufin. The use of resazurin has enabled the study of analyte oxidation reactions, such as the oxidation of dopamine and H2O2. In this report, we extend the capability of FEEM to the study of cathodic reactions using a new fluorogenic indicator, dihydroresorufin. Dihydroresorufin is a nonfluorescent molecule, which can be electrochemically oxidized to generate resorufin. The use of dihydroresorufin has enabled us to study a series of reducible analyte species including Fe(CN)63– and Ru(NH3)63+. Here we demonstrate the correlation between the simultaneously recorded fluorescence intensity of resorufin and electrochemical oxidation current during potential sweep experiments. FEEM is used to quantitatively detect the reduction of ferricyanide down to a concentration of approximately 100 μM on a 25 μm ultramicroelectrode. We also demonstrate that dihydroresorufin, as a fluorogenic indicator, gives an improved temporal response and significantly decreases diffusional broadening of the signal in FEEM as compared to resazurin.

Fluorescence-enabled electrochemical microscopy (FEEM) is demonstrated as a new technique to image transient concentration profiles of redox species generated on ultramicroelectrodes (UMEs). FEEM converts an electrical signal into an optical signal by electrically coupling a conventional redox reaction to a fluorogenic reporter reaction on a closed bipolar electrode. We describe the implementation of FEEM for diffusion layer imaging and use an array of thousands of parallel bipolar electrodes to image the diffusion layers of UMEs in two and three dimensions. This new technique provides a way to image an entire 2-dimensional lateral cross section of a dynamic diffusion layer in a single experiment. By taking several of these lateral cross sections at different axial positions in the diffusion layer, a 3-dimensional image of the diffusion layer can be built. We image the diffusion layer of a 10 μm diameter carbon fiber electrode over the course of a cyclic voltammetry experiment and compare the FEEM-generated images to concentration profiles generated from numerical simulation. We also image the diffusion layer of a two electrode array consisting of two 10 μm diameter carbon fibers over the course of a potential step experiment.

We report the preparation and characterization of single platinum and gold nanowires with lengths up to 5 millimeters. Quartz-sealed platinum and gold nanowires are fabricated by drawing a short piece of the corresponding microwire using a highly reproducible laser pulling procedure. Bare metal nanowires are prepared by hydrofluoric (HF) acid etching of the quartz encapsulation. We show that these nanowires have cylindrical shape and taper down to an observed diameter as small as 10 nm for platinum and 40 nm for gold, yielding exceptionally high aspect ratios. X-ray diffraction (XRD) analysis indicates that both the gold and platinum nanowires exhibit a significant preference for development of the {111} crystal face in the axis normal to the nanowire length, whereas the {200} crystal face is nearly absent in this axis which is supported by Transmission Electron Microscopy (TEM) analysis. Quartz-sealed nanowires can be easily manipulated and arranged into complex patterns with an increasing number of contact points. Electrical properties of single nanowires were measured at nearly 0.5 mm lengths at room temperature. Each of the samples tested was found to have a resistivity approaching the bulk metal value and high observed current densities before wire failure. The grain boundary reflection coefficient was calculated on single laser-pulled nanowires to be R = 0.616 for gold and R = 0.259 for platinum.

We report a study of the formation and quick growth of thick films of platinum oxide on platinum nanoelectrodes at low anodic potentials. Here, structurally well-defined platinum nanoelectrodes are used as a model platform for nanoscale platinum electrocatalysts. Platinum films are formed on the surface of the nanoelectrode upon application of a constant anodic potential in an acidic environment for an extended time period. A current spike is initially observed, which is attributed to capacitance charging, the oxidation of water, and the initial oxidation of the platinum surface. A finite residual current follows the initial current spike, which is composed of both water oxidation and the oxidation of platinum metal concealed beneath the growing oxide layer. These films are observed to be structurally irreversible, grow to be relatively thick, and protrude out of the glass insulating material encasing the nanoelectrode due to the added volume of the oxygen incorporated into the growing platinum oxide film. Once reduced, the platinum metal remains protruding out of the glass, and its presence is confirmed by both SEM imaging and cyclic voltammetry. Steady-state voltammetric data shows a finite increase in the diffusion-limited faradaic current of the nanoelectrode, relative to the initial steady-state current, after the oxidation/reduction of the platinum which is due to an increased area of the protruding platinum metal. A minimum apparent rate of ∼1.2 nm/min can be calculated for the growth of the platinum oxide film. The use of platinum nanoelectrodes has shown several distinct advantages in this study, including better control of the size and morphology of the individual electrocatalysts, the ability to image using electron microscopy, and the ability to use voltammetry to evaluate the geometry of the electrode quickly.

Here we report the preparation and electrochemical characterization of single Pt nanowire electrodes with radii ranging from 25 to 130 nm for their electrocatalytic activity toward the oxygen reduction reaction (ORR). Ultralong Pt nanowires were prepared by a laser pulling process. Single Pt nanowire electrodes were fabricated by metal deposition and lithography patterning to expose just a small portion (10–20 μm in length) of the nanowire for electrocatalytic studies. These wires were characterized thoroughly using cyclic voltammetry, under potential deposition of copper, and scanning electron microscopy. We have shown that their electrocatalytic activity toward ORR slightly decreases as the nanowire radius is reduced as measured by the onset potential. Additionally, the current density for the ORR decreases and the mass activity increases as the wire becomes smaller. The faradaic current was modeled on single nanowire electrodes, and the current was found to match the experimental value with outer-sphere redox species. However, significant variance was shown between the modeled ORR current and the measured value. The deviation of the ORR current on the wires is likely due to the presence of F– ions on Pt and the increased adsorption energy of oxygenated species, thus leading to a hindering of the reaction kinetics of the catalytic process. This is confirmed by Tafel plots where the slope is seen to change at a lower potential as compared to bulk polycrystalline Pt.

Here we report the use of fluorescence microscopy and closed bipolar electrodes to reveal electrochemical and electrocatalytic activity on large electrochemical arrays. We demonstrate fluorescence-enabled electrochemical microscopy (FEEM) as a new electrochemical approach for imaging transient and heterogeneous electrochemical processes. This method uses a bipolar electrode mechanism to directly couple a conventional oxidation reaction, e.g., the oxidation of ferrocene, to a special fluorogenic reduction reaction. The generation of the fluorescent product on the cathodic pole enables one to directly monitor an electrochemical process with optical microscopy. We demonstrate the use of this method on a large electrochemical array containing thousands or more parallel bipolar microelectrodes to enable spatially and temporally resolved electrochemical imaging. We first image molecular transport of a redox analyte in solution using an array containing roughly 1000 carbon fiber ultramicroelectrodes. We then carry out a simple electrocatalysis experiment to show how FEEM can be used for electrocatalyst screening. This new method could prove useful for imaging transient electrochemical events, such as fast exocytosis events on single and networks of neurons, and for parallel, high-throughput screening of new electrocatalysts.

Here we report the theory and experimental study of the steady-state voltammetric behavior of a microelectrode used as a limiting pole in a closed bipolar electrochemical cell. We show that the steady-state voltammetric response of a microelectrode used in a closed bipolar cell can be quantitatively understood by considering the responses of both poles in their respective conventional two-electrode setups. In comparison to a conventional electrochemical cell, the voltammetric response of the bipolar cell has a similar sigmoidal shape and limiting current; however, the response is often slower than that of the typical two-electrode setup. This leads to a broader voltammogram and a decreased wave slope, which can be somewhat misleading, causing the appearance that the process being studied is irreversible when it instead can be a result of the coupling of two reversible processes. We show that a large limiting current on the excess pole would facilitate the observation of a faster voltammetric response and that both redox concentration and electrode area of the excess pole affect the wave shape. Both factors should be maximized in electroanalytical experiments in order to obtain fast voltammetric responses on the main electrode of interest and to detect quick changes in analyte concentrations.

Here we report the voltammetric study of coupled electrochemical reactions on microelectrodes and nanoelectrodes in a closed bipolar cell. We use steady-state cyclic voltammetry to discuss the overall voltammetric response of closed bipolar electrodes (BPEs) and understand its dependence on the concentration of redox species and electrode size. Much of the previous work in bipolar electroanalytical chemistry has focused on the use of an “open” cell with the BPE located in an open microchannel. A closed BPE, on the other hand, has two poles placed in separate compartments and has remained relatively unexplored in this field. In this work, we demonstrated that carbon-fiber microelectrodes when backfilled with an electrolyte to establish conductivity are closed BPEs. The coupling between the oxidation reaction, e.g., dopamine oxidation, on the carbon disk/cylinder and the reduction of oxygen on the interior fiber is likely to be responsible for the conductivity. We also demonstrated the ability to quantitatively measure voltammetric properties of both the cathodic and anodic poles in a closed bipolar cell from a single cyclic voltammetry (CV) scan. It was found that “secondary” reactions such as oxygen reduction play an important role in this process. We also described the fabrication and use of Pt bipolar nanoelectrodes which may serve as a useful platform for future advances in nanoscale bipolar electrochemistry.

Here we report a new type of microelectrode sensor for single-cell exocytotic dopamine release. The new microsensor is built by forming a gold-nanoparticle (AuNP) network on a carbon fiber microelectrode. First a gold surface is obtained on a carbon fiber microdisk electrode by partially etching away the carbon followed by electrochemical deposition of gold into the pore. The gold surface is chemically functionalized with a sol−gel silicate network derived from (3-mercaptopropyl)trimethoxysilane (MPTS). A AuNP network is formed by immobilizing Au nanoparticles onto the thiol groups in the sol−gel silicate network. The AuNP-network microelectrode has been characterized by scanning electron microscopy (SEM) and steady-state voltammetry. The AuNP-network microelectrode has been used for amperometric detection of exocytotic dopamine secretion from individual pheochromocytoma (PC12) cells. The results show significant differences in the kinetic peak parameters including shorter rise time, decay time, and half-width as compared to a bare carbon fiber electrode equivalent. These results indicate AuNP-network microelectrodes possess an excellent sensing activity for single-cell exocytotic catecholamine release, specifically dopamine. Moreover, key advantageous properties inherent to bare carbon fiber microelectrodes (i.e., rigidity, flexibility, and small size) are maintained in addition to an observed prolonged shelf life stability and resistance to cellular debris fouling and dopamine polymerization.

We report the fabrication and electrochemical response of a gold nanoband electrode located at the bottom of a glass/epoxy nanotrench, hereafter referred to as a gold nanotrench electrode. Gold nanotrench electrodes of 12.5 and 40 nm in width with various depths from a few tens of nanometers to approximately 4 μm are fabricated and further characterized by cyclic voltammetry. The fabrication of a Au nanotrench electrode follows a simple electrochemical etching process in which a small AC signal is applied to an inlaid Au nanoband electrode submersed in a NaCl solution. The voltammetric behavior of a Au nanotrench electrode is characterized by a quasi-steady-state response at lower scan rates (e.g., <1 V/s for a 12.5-nm-wide electrode). We present an analytical expression for the quasi-steady-state diffusion-limited current of the nanotrench electrode based upon the analysis of the mass-transport resistance. Finite-element simulation of steady-state and transient voltammetric responses of the nanotrench electrodes provides additional insights for the analytical model. Peak-shaped transient voltammetric responses were observed at scan rates as low as 5 V/s for both inlaid and nanotrench electrodes. This result may suggest that the exposed area of the nanoband electrode is much greater than that expected from the fabrication of the inlaid bands. However, the extent to which this is seen is greatly decreased in the nanotrench electrode by a smoothing effect during etching. Our results confirm previous reports of excess overhanging metal and delamination crack contributing significantly to the shape and magnitude of the voltammetric response.

Here we report the voltammetric behavior of cone-shaped silica nanopores in quartz nanopipettes in aqueous solutions as a function of the scan rate, v. Current rectification behavior for silica nanopores with diameters in the range 4−25 nm was studied. The rectification behavior was found to be strongly dependent on the scan rate. At low scan rates (e.g., v < 1 V/s), the rectification ratio was found to be at its maximum and relatively independent of v. At high scan rates (e.g., v > 200 V/s), a nearly linear current−voltage response was obtained. In addition, the initial voltage was shown to play a critical role in the current−voltage response of cone-shaped nanopores at high scan rates. We explain this v-dependent current−voltage response by ionic redistribution in the vicinity of the nanopore mouth.

Steady-state electrochemical responses have been obtained at single Au nanoparticles using Pt nanoelectrodes. A Au single-nanoparticle electrode (SNPE) is constructed by chemically immobilizing a single Au nanoparticle at a SiO2-encapsulated Pt disk nanoelectrode, which was previously modified by an amine-terminated silane. The Au SNPE has been characterized by transmission electron microscopy, underpotential deposition of Cu, and steady-state cyclic voltammetry. It has been found that the presence of a single Au nanoparticle enhances the electron transfer from the Pt nanoelectrode to the redox molecules, and the voltammetric response at the Au SNPE depends on the size of the Au nanoparticle. The Au SNPE has been utilized to examine the oxygen-reduction reaction in a KOH solution to explore the feasibility of measuring the electrocatalytic activity at a single-nanoparticle level. It has been shown that the electrocatalytic activity of single Au nanoparticles can be directly measured using SNPEs, and the electrocatalytic activity is dependent on the size of the Au nanoparticles. This study can help to understand the structure−function relationship in nanoparticle-based electrocatalysis.

In this technical note, we report a process in scaling down the fabrication of Au disk nanoelectrodes as small as ∼4 nm in radii. We have developed a bottom-up approach toward the fabrication of individual disk-shape Au nanoelectrodes. This new approach is based upon electrochemical deposition of Au in a silica nanopore electrode and involves the following four steps. First, a laser-assisted pulling process is employed to fabricate a disk-shape Pt nanoelectrode. Second, a Pt nanopore electrode is obtained by electrochemically etching the Pt from the disk nanoelectrode. Third, a Au metal nanowire is electrochemically deposited using the Pt nanopore electrode as a template. In the last step, the Au electrode is slightly polished to expose a disk-shape Au nanoelectrode, whose size is determined by the size of the initial Pt nanoelectrode. Steady-state voltammetry in the presence of ferrocene has been used to characterize these Au nanoelectrodes. The Au nanoelectrodes are also characterized using cyclic voltammetry in a H2SO4 solution. The results show characteristic peaks corresponding to the formation of Au surface oxides and their subsequent reduction. The Au nanoelectrodes are modified with 6-(ferrocenyl)hexanethiol molecules, and cyclic voltammetry is used to characterize the ferrocene molecules attached at the Au. As an application, we have constructed Au single-nanoparticle electrodes (SNPEs) using the Au disk nanoelectrodes fabricated by electrochemical deposition. Our initial results of such SNPEs show excellent electrochemical response from single Au nanoparticles.

We present the preparation, characterization, and analytical application of silica nanochannels in the size range of 5−100 nm. These cylindrical-shaped nanochannels are prepared using a simple laser-assisted mechanical pulling process, followed by partial enclosure into a glass micropipet. The nanochannels are characterized using a combination of optical microscopy, scanning electron microscopy (SEM), and resistance measurements in an electrolyte solution. The SEM results show that the nanochannel has circular geometry at the orifice. Ohmic response has been obtained from current−voltage measurements in KCl solutions using a silica nanochannel as small as 9 nm in diameter. These nanochannels have been utilized to sense single 40 nm polystyrene nanoparticles. A linear response has been observed between the detection rate and the concentration of nanoparticles in the range of 0−25 nM. The silica nanochannels have also been applied to the study of molecular transport of double-stranded DNA. Electroosmosis-driven molecular translocation has been observed for genomic-length λ-DNA through a 9 nm nanochannel in a 3 M KCl solution.

The preparation and characterization of Pt nanoelectrodes in the range of 1 to 3 nm in radii are reported. A Pt microwire is sealed into a bilayer quartz capillary and pulled into an ultrasharp Pt nanowire sealed in a silica tip using a laser-assisted pulling process. The ultrasharp tip is then sealed into a piece of glass tubing, which is manually polished to expose the Pt. Transmission electron microscopy and steady-state voltammetry are utilized to characterize the nanoelectrodes. The results show that the minimum size of the Pt nanoelectrode is determined by the size of the Pt microwire and parameters used in the pulling process. The heterogeneous electron transfer rate constant for the oxidation of ferrocene, ferrocenemethanol, and potassium hexachloroiridate (III) are determined from steady-state voltammetry using the method of Mirkin and Bard and are found to be k° = 7.6 ± 3.4 cm/s and α = 0.85 ± 0.06 for ferrocene, k° = 7.4 ± 6.9 cm/s and α = 0.78 ± 0.16 for ferrocenemethanol, and k° = 6.0 ± 4.2 cm/s and α = 0.72 ± 0.15 for IrCl63−.