Scanning Bubble Electrochemical Microscopy: Mapping of Electrocatalytic Activity with Low-Solubility Reactants.

Determining electrocatalytic activity for reactions that involve reactants with limited solubility presents a significant challenge due to the reduced mass-transport to the electrocatalyst surface. This limitation is seen in important reactions such as the oxygen reduction reaction, nitrogen reduction reaction, and carbon dioxide reduction reaction. We introduce a new approach, which we call scanning bubble electrochemical microscopy, to enable the detection and high-resolution mapping of electrocatalytic activity with low-solubility reactants at high mass-transport rates. Using a scanning probe approach, a dual-barreled nanopipette is used to precisely deliver the gas-phase reactant within micrometers of an electrocatalyst surface, which results in high mass-transport rates at the electrocatalyst surface directly under the probe. We demonstrate the scanning bubble electrochemical microscopy approach by mapping the oxygen reduction reaction on model platinum microelectrode surfaces. We anticipate that scanning bubble electrochemical microscopy will provide an effective tool for measuring the electrocatalytic activity of reactants that have limited solubility.

Electrochemical Detection of Tenofovir through Quenching of Chloride Ion-Mediated Gold Electrodissolution.

Tenofovir (TNF) is a nucleotide reverse transcriptase inhibitor used as an antiviral medication to treat human immunodeficiency virus (HIV) and hepatitis B virus infections. The extensive use of TNF can result in its release into the environment, and there is growing interest in developing simple and cost-effective methods for detecting TNF. We report that the electrochemical dissolution of gold in a chloride ion-containing electrolyte is suppressed in the presence of TNF. The quenching of the gold electrodissolution response is the result of the adsorption of TNF onto the gold surface. A simple analysis shows that we can relate the degree of TNF surface coverage to the relative size of the quenching of the gold electrodissolution response and follow the time-dependent absorption of TNF onto the gold electrode surface.

Isolation of pseudocapacitive surface processes at monolayer MXene flakes reveals delocalized charging mechanism.

Pseudocapacitive charge storage in Ti3C2Tx MXenes in acid electrolytes is typically described as involving proton intercalation/deintercalation accompanied by redox switching of the Ti centres and protonation/deprotonation of oxygen functional groups. Here we conduct nanoscale electrochemical measurements in a unique experimental configuration, restricting the electrochemical contact area to a small subregion (0.3 µm2) of a monolayer Ti3C2Tx flake. In this unique configuration, proton intercalation into interlayer spaces is not possible, and surface processes are isolated from the bulk processes, characteristic of macroscale electrodes. Analysis of the pseudocapacitive response of differently sized MXene flakes indicates that entire MXene flakes are charged through electrochemical contact of only a small basal plane subregion, corresponding to as little as 3% of the flake surface area. Our observation of pseudocapacitive charging outside the electrochemical contact area is suggestive of a fast transport of protons mechanism across the MXene surface.

Partially oxidised boron nitride as a 2D nanomaterial for nanofiltration applications.

Boron nitride (BN) based 2D nanomaterials are an emerging class of materials for the development of new membranes for nanofiltration applications. Here, we report the preparation, characterisation and testing of highly promising nanofiltration membranes produced from partially oxidised BN (BNOx) 2D nanosheets. In our work, the partial oxidation of BN was successfully achieved by heating the bulk h-BN powder in air at 1000 °C, resulting in BNOx product. The characterisation of the sample showed the presence of B-OH groups corresponding to the partial oxidisation of the BN. The BNOx material was then exfoliated in water and used to produce membranes, using vacuum filtration. These membranes were characterised using electron microscopy, BET and mercury porosimetry techniques. The membranes have also been tested in water purification and removal of several typical water-soluble dyes, demonstrating outstanding retention values close to 100%. We believe that this research opens up new opportunities for further production, as well as chemical functionalisation and modification of membranes for nanofiltration and separation technologies.

High-Performance Boron Nitride-Based Membranes for Water Purification.

In recent years, nanotechnology-based approaches have resulted in the development of new alternative sustainable technologies for water purification. Two-dimensional (2D) nanomaterials are an emerging class of materials for nanofiltration membranes. In this work, we report the production, characterisation and testing of a promising nanofiltration membrane made from water-exfoliated boron nitride (BN) 2D nanosheets. The membranes have been tested for water purification and removal of typical water-soluble dyes such as methyl orange, methylene blue and Evans blue, with the water-exfoliated BN membranes achieving retention values close to 100%. In addition, we compared the performance of membranes made from water-exfoliated BN with those produced from BN using sonication-assisted liquid exfoliation in selected organic solvents such as 2-propanol and N-methyl-2-pyrrolidone. It was found that membranes from the water-exfoliated BN showed superior performance. We believe this research opens up a unique opportunity for the development of new high-performance environmentally friendly membranes for nanofiltration and new sustainable separation technologies.

Enhancing Lithium Insertion with Electrostatic Nanoconfinement in a Lithography Patterned Precision Cell.

The rapidly growing demand for portable electronics, electric vehicles, and grid storage drives the pursuit of high-performance electrical energy storage (EES). A key strategy for improving EES performance is exploiting nanostructured electrodes that present nanoconfined environments of adjacent electrolytes, with the goal to decrease ion diffusion paths and increase active surface areas. However, fundamental gaps persist in understanding the interface-governed electrochemistry in such nanoconfined geometries, in part because of the imprecise and variable dimension control. Here, we report quantification of lithium insertion under nanoconfinement of the electrolyte in a precise lithography-patterned nanofluidic cell. We show a mechanism that enhances ion insertion under nanoconfinement, namely, selective ion accumulation when the confinement length is comparable to the electrical double layer thickness. The nanofabrication approach with uniform and accurate dimensional control provides a versatile model system to explore fundamental mechanisms of nanoscale electrochemistry, which could have an impact on practical energy storage systems.

Single Ag nanoparticle collisions within a dual-electrode micro-gap cell.

An adjustable width (between 600 nm and 20 µm) gap between two Au microelectrodes is used to probe the electrodissolution dynamics of single Ag nanoparticles. One Au microelectrode is used to drive the oxidation and subsequent dissolution of a single Ag nanoparticle, which displays a multi-peak oxidation behavior, while a second Au microelectrode is used to collect the Ag+ that is produced. Careful analysis of the high temporal resolution current-time traces reveals capacitive coupling between electrodes due to the sudden injection of Ag+ ions into the gap between the electrodes. The current-time traces allow measurement of the effect of citrate concentration on the electrodissolution dynamics of a single Ag nanoparticle, which reveals that the presence of 2 mM citrate significantly slows down the release of Ag+. Intriguingly, these experiments also reveal that only a portion (ca. 50%) of the oxidized Ag nanoparticle is released as free Ag+ regardless of citrate concentration.

Method for Dynamically Detecting Secretions from Single Cells Using a Nanopore.

Secreted proteins mediate cell-to-cell communications. Thus, eavesdropping on the secretome could reveal the cellular phenotype, but it is challenging to detect the proteins because they are secreted only in minute amounts and then diluted in blood plasma or contaminated by cell culture medium or the lysate. In this pilot study, it is demonstrated that secretions from single cancer cells can be detected and dynamically analyzed through measurements of blockades in the electrolytic current due to single molecules translocating through a nanopore in a thin inorganic membrane. It is established that the distribution of blockades can be used to differentiate three different cancer cell lines (U937, MDA-MB-231, and MCF-7) in real time and quickly (<20 s). Importantly, the distinctive blockades associated with the chemokine CCL5, a prognostic factor for disease progression in breast cancer, along with other low-mass biomarkers of breast cancer (PI3, TIMP1, and MMP1) were identified in the context of the secretome of these three cell types, tracked with time, and used to provide information on the cellular phenotype.

Selective increase in CO2 electroreduction activity at grain-boundary surface terminations.

Altering a material's catalytic properties requires identifying structural features that give rise to active surfaces. Grain boundaries create strained regions in polycrystalline materials by stabilizing dislocations and may provide a way to create high-energy surfaces for catalysis that are kinetically trapped. Although grain-boundary density has previously been correlated with catalytic activity for some reactions, direct evidence that grain boundaries create surfaces with enhanced activity is lacking. We used a combination of bulk electrochemical measurements and scanning electrochemical cell microscopy with submicrometer resolution to show that grain-boundary surface terminations in gold electrodes are more active than grain surfaces for electrochemical carbon dioxide (CO2) reduction to carbon monoxide (CO) but not for the competing hydrogen (H2) evolution reaction. The catalytic footprint of the grain boundary is commensurate with its dislocation-induced strain field, providing a strategy for broader exploitation of grain-boundary effects in heterogeneous catalysis.

Three-Dimensional Super-resolution Imaging of Single Nanoparticles Delivered by Pipettes.

Controlled three-dimensional positioning of nanoparticles is achieved by delivering single fluorescent nanoparticles from a nanopipette and capturing them at well-defined regions of an electrified substrate. To control the position of single nanoparticles, the force of the pressure-driven flow from the pipette is balanced by the attractive electrostatic force at the substrate, providing a strategy by which nanoparticle trajectories can be manipulated in real time. To visualize nanoparticle motion, a resistive-pulse electrochemical setup is coupled with an optical microscope, and nanoparticle trajectories are tracked in three dimensions using super-resolution fluorescence imaging to obtain positional information with precision in the tens of nanometers. As the particles approach the substrate, the diffusion kinetics are analyzed and reveal either subdiffusive (hindered) or superdiffusive (directed) motion depending on the electric field at the substrate and the pressure-driven flow from the pipette. By balancing the effects of the forces exerted on the particle by the pressure and electric fields, controlled, real-time manipulation of single nanoparticle trajectories is achieved. The developed approach has implications for a variety of applications such as surface patterning and drug delivery using colloidal nanoparticles.

Fabrication, Testing, and Simulation of All-Solid-State Three-Dimensional Li-Ion Batteries.

Demonstration of three-dimensional all-solid-state Li-ion batteries (3D SSLIBs) has been a long-standing goal for numerous researchers in the battery community interested in developing high power and high areal energy density storage solutions for a variety of applications. Ideally, the 3D geometry maximizes the volume of active material per unit area, while keeping its thickness small to allow for fast Li diffusion. In this paper, we describe experimental testing and simulation of 3D SSLIBs fabricated using materials and thin-film deposition methods compatible with semiconductor device processing. These 3D SSLIBs consist of Si microcolumns onto which the battery layers are sequentially deposited using physical vapor deposition. The power performance of the 3D SSLIBs lags significantly behind that of similarly prepared planar SSLIBs. Analysis of the experimental results using finite element modeling indicates that the origin of the poor power performance is the structural inhomogeneity of the 3D SSLIB, coupled with low electrolyte ionic conductivity and diffusion rate in the cathode, which lead to highly nonuniform internal current density distribution and poor cathode utilization.

Resistive Pulse Delivery of Single Nanoparticles to Electrochemical Interfaces.

An experimental system for controlling and interrogating the collisions of individual nanoparticles at electrode/electrolyte interfaces is described. A nanopipet positioned over a 400 nm radius Pt ultramicroelectrode is used to deliver individual nanoparticles, via pressure-driven solution flow, to the underlying electrode, where the nanoparticles undergo collisions and are detected electrochemically. High-velocity collisions result in elastic collisions of negatively charged polystyrene nanospheres at the Pt/water interface, while low-velocity collisions result in nanoparticle adsorption ("sticky" collisions). The ability to position the nanopipet with respect to the underlying ultramicroelectrode also allows the time between particle release from the nanopipet and electrode collision to be investigated as a function of nanopipet-electrode separation, d. The time between release and collision of the nanoparticle is found to be proportional to d3, in excellent agreement with an analytical expression for convective fluid flow from a pipet orifice.

Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient.

Simultaneous Interfacial Reactivity and Topography Mapping with Scanning Ion Conductance Microscopy.

Scanning ion conductance microscopy (SICM) is a powerful technique for imaging the topography of a wide range of materials and interfaces. In this report, we develop the use and scope of SICM, showing how it can be used for mapping spatial distributions of ionic fluxes due to (electro)chemical reactions occurring at interfaces. The basic idea is that there is a change of ion conductance inside a nanopipet probe when it approaches an active site, where the ionic composition is different to that in bulk solution, and this can be sensed via the current flow in the nanopipet with an applied bias. Careful tuning of the tip potential allows the current response to be sensitive to either topography or activity, if desired. Furthermore, the use of a distance modulation SICM scheme allows reasonably faithful probe positioning using the resulting ac response, irrespective of whether there is a reaction at the interface that changes the local ionic composition. Both strategies (distance modulation or tuned bias) allow simultaneous topography-activity mapping with a single channel probe. The application of SICM reaction imaging is demonstrated on several examples, including voltammetric mapping of electrocatalytic reactions on electrodes and high-speed electrochemical imaging at rates approaching 4 s per image frame. These two distinct approaches provide movies of electrochemical current as a function of potential with hundreds of frames (images) of surface reactivity, to reveal a wealth of spatially resolved information on potential- (and time) dependent electrochemical phenomena. The experimental studies are supported by detailed finite element method modeling that places the technique on a quantitative footing.

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.

High-Speed Electrochemical Imaging.

The design, development, and application of high-speed scanning electrochemical probe microscopy is reported. The approach allows the acquisition of a series of high-resolution images (typically 1000 pixels µm(-2)) at rates approaching 4 seconds per frame, while collecting up to 8000 image pixels per second, about 1000 times faster than typical imaging speeds used up to now. The focus is on scanning electrochemical cell microscopy (SECCM), but the principles and practicalities are applicable to many electrochemical imaging methods. The versatility of the high-speed scan concept is demonstrated at a variety of substrates, including imaging the electroactivity of a patterned self-assembled monolayer on gold, visualization of chemical reactions occurring at single wall carbon nanotubes, and probing nanoscale electrocatalysts for water splitting. These studies provide movies of spatial variations of electrochemical fluxes as a function of potential and a platform for the further development of high speed scanning with other electrochemical imaging techniques.