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Nanoelectrochemistry, where electrochemical processes are controlled and investigated with nanoscale resolution, is gaining more and more attention because of the many potential applications in energy and sensing and the fact that there is much to learn about fundamental electrochemical processes when we explore them at the nanoscale. The development of instrumental methods that can explore the heterogeneity of electrochemistry occurring across an electrode surface, monitoring single molecules or many single nanoparticles on a surface simultaneously, have been pivotal in giving us new insights into nanoscale electrochemistry. Equally important has been the ability to synthesise or fabricate nanoscale entities with a high degree of control that allows us to develop nanoscale devices. Central to the latter has been the incredible advances in nanomaterial synthesis where electrode materials with atomic control over electrochemically active sites can be achieved. After introducing nanoelectrochemistry, this paper focuses on recent developments in two major application areas of nanoelectrochemistry; electrocatalysis and using single entities in sensing. Discussion of the developments in these two application fields highlights some of the advances in the fundamental understanding of nanoelectrochemical systems really driving these applications forward. Looking into our nanocrystal ball, this paper then highlights: the need to understand the impact of nanoconfinement on electrochemical processes, the need to measure many single entities, the need to develop more sophisticated ways of treating the potentially large data sets from measuring such many single entities, the need for more new methods for characterising nanoelectrochemical systems as they operate and the need for material synthesis to become more reproducible as well as possess more nanoscale control.

At the most fundamental level, the behavior of tissue is governed by the activity of its single cells. A detailed examination of single-cell biology is necessary in order to gain a deeper understanding of disease progression. While single-cell genomics and transcriptomics are mature due to robust amplification strategies, the metabolome is difficult to quantify. Nanoelectrochemical techniques stand poised to quantify single-cell metabolism as a result of the fabrication of nanoelectrodes, which allow one to make intracellular electrochemical measurements. This article is concerned with intracellular nanoelectrochemistry, focusing on the sensitive and selective quantification of various metabolites within a single, living cell. We will review the strong literature behind this field, discuss the potential deleterious effects of passing charge inside cells, and provide future outlooks for this promising avenue of inquiry. We also present a mathematical relationship based on Faraday's Law and bulk electrolysis theory to examine the consumption of analyte within a cell due to passing charge at the nanotip.Graphical abstract.

Label-free biosensing has been the dream of scientists and biotechnologists as reported by Vollmer and Arnold (Nat Methods 5:591-596, 2008). The ability of examining living cells is crucial to cell biology as noted by Fang (Int J Electrochem 2011:460850, 2011). Chemical measurement with electrodes is label-free and has demonstrated capability of studying living cells. In recent years, nanoelectrodes of different functionality have been developed. These nanometer-sized electrodes, coupled with scanning electrochemical microscopy (SECM), have further enabled nanometer spatial resolution study in aqueous environments. Developments in the field of nanoelectrochemistry have allowed measurement of signaling species at single cells, contributing to better understanding of cell biology. Leading studies using nanoelectrochemistry of a variety of cellular signaling molecules, including redox-active neurotransmitter (e.g., dopamine), non-redox-active neurotransmitter (e.g., acetylcholine), reactive oxygen species (ROS), and reactive nitrogen species (RNS), are reviewed here.

Summary Conventional polyolefin separators suffer from poor wettability to liquid electrolytes (LEs). Although some modified separators exhibit improved wettability, they are hydrophilic, causing inevitable moisture uptake. Trace water could result in poor performance and safety hazard of Li metal batteries. Here, we report a design idea of superLEphilic/superhydrophobic and thermostable separators by modifying the Celgard separator using silicone nanofilaments. The separator features low moisture uptake (∼0%), fast LE diffusion (454 ms), and high LE uptake (287.8%), LE retention rate, and Li+ conductivity. Consequently, the Li/LiFePO4 cells show high cycling stability (96.05% after 350 cycles), good rate performance (125 mA h g−1 at 5.0 C), low resistance, and stable open circuit voltage at 160°C. Moreover, the separator could improve performance of the other Li metal batteries with high-voltage cathodes and the LiFePO4/graphite pouch cells. This work provides an avenue for designing advanced separators by using bioinspired superwetting surfaces., Graphical Abstract, Highlights • A superLEphilic/superhydrophobic separator is first reported for Li metal batteries • The separator has low moisture uptake and could improve performance of Li/Li cells • The separator features fast LE diffusion, high LE uptake, and Li+ conductivity • The separator could enhance performance of high-voltage Li metal batteries, Chemistry; Electrochemistry; Nanoelectrochemistry; Materials Science; Energy Materials

In this work, we demonstrate an alteration of mechanical, electrophysical, piezo- and ferroelectric properties of polyvinylidene fluoride/trifluoroethylene P(VDF-TrFE) copolymer at the composition of 70/30 mol% in the presence of lithium niobate (LiNbO3) fillers. The micro- and nanoscale measurements of the elastic modulus suggest a two-fold increase in the mechanical rigidity of the P(VDF-TrFE) film after embedding the LiNbO3. The enhancement of local piezo- and ferroelectric properties of the modified polymer is evidenced by the increase of the direct piezoelectric coefficient from 27.1 pm/V to 36.1 pm/V. This increase is supposed to be associated with a significant contribution from Li-ion diffusion (the surface nanoelectrochemistry effect). This suggestion is supported by the observation of irreversible dc bias voltage-induced Li-ion extraction contributing to the locally-measured piezoresponse. The dynamics of the Li-ion diffusion, studied by electrochemical strain time spectroscopy, shows a decrease of the diffusion coefficient for an area poled by dc bias voltage as compared with a pristine one. This decrease confirms the existence of irreversible electrochemical processes during the local piezoelectric measurements. At the same time, X-ray diffraction and micro-Raman data suggest the integrity of the intramolecular structure of the P(VDF-TrFE) copolymer after embedding the LiNbO3 fillers. This is a key achievement allowing to keep the structure-related parameters specific to the pure P(VDF-TrFE) copolymer. The obtained results reveal a crucial role of the fillers in attaining the desired functional behavior, thus paving the way towards the development of advanced sensors, transducers, actuators, and piezoelectric devices.

International audience; This opinion paper details three typical cases in which new theoretical concepts need to be implemented in molecular electrochemistry in order to rationalize experimental results obtained in nanoscale cells or performed in new electrolytic media such as RTILs.

The active materials constitute the heart of any battery so that unambiguous determination of their intrinsic properties is of essential importance to achieve progress in battery research. A variety of in situ techniques with high lateral resolution has been developed or adapted for battery research. Surprisingly, nanoelectrochemistry is not attracting sufficient attention from the battery community despite the existing examples of relevant in situ and highly resolved spatiotemporal information. Herein, the important role of nanoelectrochemistry in battery research is highlighted to help encourage its use in this field. In the first part, two examples in which the use of nanoelectrochemistry is a must are provided, that is, determination of intrinsic kinetics of active materials and understanding of relationships between particle structure and electrochemical activity. In the second part, pros and cons of three mature nanoelectrochemistry techniques in battery research, that is, particle-on-a-stick measurements, nanoimpact measurements, and scanning electrochemical probe microscopy, are discussed providing representative examples., Spanish Government (MINECO) through the Research Challenges Programme (grant RTI2018-099228-A-I00) and Ramón y Cajal award (RYC2018-026086-I) as well as the NanoBat project. NanoBat has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 861962.

Deterministic positioning and assembly of colloidal nanoparticles (NPs) onto substrates is a core requirement and a promising alternative to top down lithography to create functional nanostructures and nanodevices with intriguing optical, electrical, and catalytic features. Capillary-assisted particle assembly (CAPA) has emerged as an attractive technique to this end, as it allows controlled and selective assembly of a wide variety of NPs onto predefined topographical templates using capillary forces. One critical issue with CAPA, however, lies in its final printing step, where high printing yields are possible only with the use of an adhesive polymer film. To address this problem, we have developed a template dissolution interfacial patterning (TDIP) technique to assemble and print single colloidal AuNP arrays onto various dielectric and conductive substrates in the absence of any adhesion layer, with printing yields higher than 98%. The TDIP approach grants direct access to the interface between the AuNP and the target surface, enabling the use of colloidal AuNPs as building blocks for practical applications. The versatile applicability of TDIP is demonstrated by the creation of direct electrical junctions for electro- and photoelectrochemistry and nanoparticle-on-mirror geometries for single particle molecular sensing.

Summary The carbon-free production of hydrogen from water splitting holds grand promise for the critical energy and environmental challenges. Herein, few-atomic-layers iron (FeFAL) anchored on GaN nanowire arrays (NWs) is demonstrated as a highly active hydrogen evolution reaction catalyst, attributing to the spatial confinement and the nitrogen-terminated surface of GaN NWs. Based on density functional theory calculations, the hydrogen adsorption on FeFAL:GaN NWs is found to exhibit a significantly low free energy of −0.13 eV, indicative of high activity. Meanwhile, its outstanding optoelectronic properties are realized by the strong electronic coupling between atomic iron layers and GaN(10ī0) together with the nearly defect-free GaN NWs. As a result, FeFAL:GaN NWs/n+-p Si exhibits a prominent current density of ∼ −30 mA cm−2 at an overpotential of ∼0.2 V versus reversible hydrogen electrode with a decent onset potential of +0.35 V and 98% Faradaic efficiency in 0.5 mol/L KHCO3 aqueous solution under standard one-sun illumination., Graphical Abstract, Highlights • Few-atomic-layers iron was anchored on GaN nanowires as an efficient HER catalyst • The spatial-confinement and N-rich GaN is essential for forming atomic iron layers • Low hydrogen absorption free energy is theoretically revealed over Fe3L:GaN • The device exhibits a prominent performance for PEC water splitting to H2, Catalysis; Electrochemical Energy Production; Nanoelectrochemistry; Atomic Electronic Structure; Nanomaterials

International audience; Electrochemical blocking is a type of single-entity electrochemical measurement particularly well adapted to the detection of insulating particles. The digital detection of ultralow concentrations of artificial entities such as polymer particles or biotargets such as proteins and bacteria represents an exceptional opportunity for sensing applications. In this review, we explore the latest development in the field of electrochemical blocking and propose some perspectives.

Summary The key properties of yolk-shell architecture in improving electrochemical performance lies in its uniformity and the appropriate void space, which can expand/contract freely upon lithium alloying and leaching without damaging the outer shell, while being achievable with minimal sacrifice of volumetric energy density. Therefore, we developed a highly controllable strategy to fabricate a uniform porous germanium@polypyrrole (PGe@PPy) yolk-shell architecture with conformal Al2O3 sacrificial layer by atomic layer deposition (ALD) process. The PGe@PPy yolk-shell anode fabricated with 300 ALD cycles delivers excellent electrochemical performance: high reversible capacity (1,220 mA hr g−1), long cycle performance (>95% capacity retention after 1,000 cycles), and excellent rate capability (>750 mA hr g−1 at 32 A g−1). Electrodes with high areal capacity and current density were also successfully fabricated, opening a new pathway to develop high-capacity electrode materials with large volume expansion., Graphical Abstract, Highlights • Porous germanium@polypyrrole (PGe@PPy) yolk-shell architecture was developed • Precision expansion and void control make PGe@PPy stable during lithiation/delithiation • PGe@PPy electrode shows high rate and areal capacity, cycling stability, and current density • The full cell shows the stable capacity retention with high energy density, Nanoparticles; Nanoelectrochemistry; Materials Science; Energy Materials

Lithium (Li) dendrite formation is one of the major hurdles limiting the development of Li-metal batteries, including Li-O2 batteries. Herein, we report the first observation of the dendrite-free epitaxial growth of a Li metal up to 10-μm thick during charging (plating) in the LiBr-LiNO3 dual anion electrolyte under O2 atmosphere. This phenomenon is due to the formation of an ultrathin and homogeneous Li2 O-rich solid-electrolyte interphase (SEI) layer in the preceding discharge (stripping) process, where the corrosive nature of Br- seems to give rise to remove the original incompact passivation layer and NO3- oxidizes (passivates) the freshly formed Li surface to prevent further reactions with the electrolyte. Such reactions keep the SEI thin (

Electrochemistry at confinement plays a significant impact on single entity analysis, efficient energy conversion, and nanofluidic transportation. Usually, the confinement is constructed by nanopore-structured materials. However, the physicochemical properties of function elements at inner walls of nanopore are inexplicit due to the limit of technology, which hinders the elegant modifications of nanopores and their related sophisticated applications. To address this issue, Xia and coworkers from China University of Geosciences developed a new solid-state nanochannel system modified with only function elements at outer surface. Explicit regulation of ion transport across this system was realized by the precise measurement of the physicochemical properties of function elements at the outer surface, which was further supported by the numerical simulations. Furthermore, this novel system shows advantages in osmotic energy conversion and universal sensing of targets from ions to cells. The corresponding research has been published in Nature Communications and can be accessed at https://doi.org/10.1038/s41467-021-21507-7 .

Low dimensional materials exhibit distinct properties compared to their bulk counterparts. A plethora of examples have been demonstrated in two-dimensional (2-D) materials, including graphene and transition metal dichalcogenides (TMDCs). These novel and intriguing properties at the nano-, molecular- and even monatomic scales have triggered tremendous interest and research, from fundamental studies to practical applications and even device fabrication. The unique behaviors of 2-D materials result from the special structure–property relationships that exist between surface topographical variations and mechanical responses, electronic structures, optical characteristics, and electrochemical properties. These relationships are generally convoluted and sensitive to ambient and external perturbations. Characterizing these systems thus requires techniques capable of providing multidimensional information under controlled environments, such as atomic force microscopy (AFM). Today, AFM plays a key role in exploring the basic principles underlying the functionality of 2-D materials. In this tutorial review, we provide a brief introduction to some of the unique properties of 2-D materials, followed by a summary of the basic principles of AFM and the various AFM modes most appropriate for studying these systems. Following that, we will focus on five important properties of 2-D materials and their characterization in more detail, including recent literature examples. These properties include nanomechanics, nanoelectromechanics, nanoelectrics, nanospectroscopy, and nanoelectrochemistry.

Nanomaterials exhibit structural and functional heterogeneity among individual nanoparticles, thus requiring a capability to study single nanoparticles. While electron microscopes often provide static images of their chemical composition, morphology and structure, imaging the chemical activity of single nanoparticles is highly desirable for exploring the structure-activity relationship via a bottom-up strategy, to understand their microscopic reaction mechanisms and kinetics, and to identify a minority subpopulation with extraordinary activity. Recently, various optical microscopes have been emerging as powerful techniques towards this goal, owing to their non-invasive nature, excellent sensitivity, diversified spectroscopic principles and sufficient spatial and temporal resolution. In this review, we first introduce the motivational concept and the strength of using optical microscopy to study the chemical activity of single nanoparticles. In the second section, five types of commonly used optical microscopy, fluorescence microscopy, dark-field microscopy, surface plasmon resonance microscopy, Raman microscopy and photothermal microscopy are described, with an emphasis on their applicable nanomaterials and mechanisms for application. Recent achievements of these techniques in nanosensing, nanoelectrochemistry and nanocatalysis are surveyed and summarized in the subsequent sections, respectively. We finally conclude with our perspective on the remaining challenges and the future trends in this field.

Clarifying the hidden but intrinsic feature of single nanoparticles by nanoelectrochemistry could help understand its potential for diverse applications. The uncontrolled interface and bandwidth limitation in the electrochemical measurement put the obstacle in single particle collision. Here, we demonstrate a well-defined 30 nm nanopore electrode with a rapid chemical-electrochemical fabrication method which provides a high reproducibility in both size and performance. A capacitance-based detection mechanism is demonstrated to achieve a high current resolution of 0.6 pA ±0.1 pA (RMS) and a high the temporal resolution of 0.01 ms. By utilizing this electrode, the dynamic interactions of every single particle in the mixture could be directly read during the collision process. The collision frequency is two orders of magnitude higher than previous reports, which helps reveal the hidden features of nanoparticles during the complex and multidimensional interaction processes.

Despite significant advancement in preparing various hollow structures by Ostwald ripening, one common problem is the intractable uncontrollability of initiating Ostwald ripening due to the complexity of the reaction processes. Here, a new strategy on Hansen solubility parameter (HSP)-guided solvent selection to initiate Ostwald ripening is proposed. Based on this comprehensive principle for solvent optimization, N,N-dimethylformamide (DMF) was screened out, achieving accurate synthesis of interior space-tunable MoSe2 spherical structures (solid, core-shell, yolk-shell and hollow spheres). The resultant MoSe2 structures exhibit architecture-dependent electrochemical performances towards hydrogen evolution reaction and sodium-ion batteries. This pre-solvent selection strategy can effectively provide researchers great possibility in efficiently synthesizing various hollow structures. This work paves a new pathway for deeply understanding Ostwald ripening.

Recent literature has evinced a keen interest in porous electrodes. Numerous applications have been discussed and some aspects of the voltammetry investigated, a theoretical description of adsorption- and desorption processes though remains largely absent. The present study fills this important gap and provides a detailed analysis of the impact of adsorption on voltammetric electrode responses in porous materials. It is shown that in some cases, adsorption- and desorption processes may aid the detection of analytes while in other cases a planar unmodified electrode is superior in performance. Finally practical conclusions are drawn for the design of future experimental systems.

We study in real time the optical response of individual plasmonic nanoparticles on a mirror, utilized as electrodes in an electrochemical cell when a voltage is applied. In this geometry, Au nanoparticles are separated from a bulk Au film by an ultrathin molecular spacer. The nanoscale plasmonic hotspot underneath the nanoparticles locally reveals the modified charge on the Au surface and changes in the polarizability of the molecular spacer. Dark-field and Raman spectroscopy performed on the same nanoparticle show our ability to exploit isolated plasmonic junctions to track the dynamics of nanoelectrochemistry. Enhancements in Raman emission and blue-shifts at a negative potential show the ability to shift electrons within the gap molecules.

Hybrid magnetite/carbon quantum dots (MagNP/C-dots) were prepared and their characterization performed by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Because of their suitable magnetization and electrochemical properties, they were used as versatile electrode modifiers after magnetically confining onto screen printed carbon electrodes (SPE), with the aid of a miniature external magnet. The reported strategy introduces a convenient procedure for assembling modified electrodes, since the nanoparticles can be easily released by removing the magnet. The non-enzymatic magnetic biosensor showed excellent performance in the determination of NADH at the concentration range 2×10−7 to 5×10−6 mol L−1, exhibiting a sensitivity of 0.15 μmol L−1 and detection limit of 20 nmol L−1. The MagNP/C-dots /SPE sensor was also successfully applied for the determination of NADH in serum samples. The interference of typical biological molecules has also been investigated.

Near-infrared electrochemiluminescence (ECL) from Au-thiolate nanoclusters is activated by electrode reactions and enhanced by ethylenediamine tetraacetic acid (EDTA). The enhancement effect is higher at pH 7.4 than at more basic or acidic pHs. Magnesium ions are found to modulate the ECL signals through complexation with EDTA and the interaction with the Au nanoclusters. The chemical system and the signal modulation mechanism are believed to be generalizable and advantageous for future sensing and analysis applications with the following merits: 1) Ambient ECL without oxygen removal, 2) high enhancement at physiological pH values, 3) in the near-IR spectrum window with low interference, 4) rich and tunable redox activity of the Au nanoclusters, and 5) EDTA representing other ionophores or chelaters as versatile coreactants.

[Image: see text] Mass spectrometry imaging is a field that promises to become a mainstream bioanalysis technology by allowing the combination of single-cell imaging and subcellular quantitative analysis. The frontier of single-cell imaging has advanced to the point where it is now possible to compare the chemical contents of individual organelles in terms of raw or normalized ion signal. However, to realize the full potential of this technology, it is necessary to move beyond this concept of relative quantification. Here we present a nanoSIMS imaging method that directly measures the absolute concentration of an organelle-associated, isotopically labeled, pro-drug directly from a mass spectrometry image. This is validated with a recently developed nanoelectrochemistry method for single organelles. We establish a limit of detection based on the number of isotopic labels used and the volume of the organelle of interest, also offering this calculation as a web application. This approach allows subcellular quantification of drugs and metabolites, an overarching and previously unmet goal in cell science and pharmaceutical development.

In recent years, on-chip nano-electrodes have enabled electrochemical analytical sensors that exhibit enhanced performance. These on-chip sensors have tremendous potential for application in Manufacturing 4.0 paradigms. A key challenge with these sensors is that electric fields, associated with biased interconnection tracks, can induce charge build-up in the electrolyte solution leading to undesirable charging currents superimposed on the Faradaic signals. During in-line measurements, it is very difficult to apply background subtraction techniques accurately; due to variations with time in buffering capacity, flow rate, electrolyte concentration etc. To address this challenge, we explore integration of an on-chip Faraday shield to block and reduce, as much as possible, the formation of these charging currents. Using this approach, we demonstrate a significant reduction in charging current at applied scan rates up to 50 V.s-1

Measuring the intrinsic features of single nanoparticles by nanoelectrochemistry holds deep fundamental importance and has potential impacts in nanoscience. However, electrochemically analyzing single nanoparticles is challenging, as the sensing nanointerface is uncontrollable. To address this challenge, we describe here the fabrication and characterization of a closed-type wireless nanopore electrode (WNE) that exhibits a highly controllable morphology and outstanding reproducibility. The facile fabrication of WNE enables the preparation of well-defined nanoelectrodes in a general chemistry laboratory without the use of a clean room and expensive equipment. One application of a 30 nm closed-type WNE in analysis of single gold nanoparticles in the mixture is also highlighted, which shows a high current resolution of 0.6 pA and high temporal resolution of 0.01 ms. Accompanied by their excellent morphology and small diameters, more potential applications of closed-type WNEs can be expanded from nanoparticle characterization to single molecule/ion detection and single-cell probing.

Summary Electrosynthesis is to use electricity to drive chemical reactions for chemical synthesis and is potentially a green approach to fuel and energy sustainability. Nanostructured catalysts play an important role in promoting electrochemical reactions under green chemistry conditions. This perspective first provides a brief tutorial on electrosynthesis and the roles the nanocatalysts play in the synthesis. It then outlines the common strategies used to develop nanocatalysts for hydrogen evolution reaction, CO2 reduction reaction, and biomass upgrading. The perspective further summarizes the current methodologies that have been developed for scaling-up synthesis of nanocatalysts, which will be essential for the electrosynthesis to become a viable industry approach., Graphical abstract, Catalysis; nanoelectrochemistry; chemical synthesis; nanostructure

International audience; Nanoparticles (NPs) based electrochemical devices are generating a growing interest and optical microscopy has recently proven to be a powerful tool to apprehend their electrochemical behavior. Through several striking examples, this review demonstrates how label-free optical imaging coupled to an electrochemical actuation can be used to probe operando the physical and electrochemical properties of single NPs, with high resolution and sensitivity and without additional emitters. Such an approach can be particularly relevant to establish clear structure-motion/reactivity relationships required to optimize NPs exploited as electrode materials.

One frontier of measurement science is pushing the limit of what is measurable. Nanoelectrochemistry has transformed what is measurable at the nanoscale, elucidating reactivity of single atoms, molecules, and nanoparticles, one by one. The ability to interrogate physicochemical properties of single entities has elucidated new truths of nature that are otherwise averaged out during measurements over many entities (ensemble experiments). Single-entity experiments also give access to the ultimate sensitivity in measurement science: the specific detection of one single entity (not nanomolar quantities, not picomolar quantities—one single unit). One exciting subset of single-entity electrochemistry, and the topic of this review, is the study of reactions in nanoreactors of subfemtoliter (10−15 L) volumes with a particular focus on nanoparticle synthesis.

In this work, we develop a Bottom-Up Electrochemical Fabrication process of Conjugated Ultrathin Layers with Tailored switchable properties. To do so, we use ultrathin layers of covalently grafted oligo(bisthienylbenzene) (oligo(BTB)) as a switchable organic electrodes and perform 3,4-ethylenedioxythiophene (EDOT) oxidation on such organic layer. Adding only 3 nm of EDOT moieties (5 to 6 units) completely changes the switching properties of the layer without changing the surface concentration of the grafted electroactive species. As a consequence, a range of new materials, with tunable interfacial properties, is created through this bottom-up electrochemical process. They consist of oligo(BTB)-oligo(EDOT) di-block oligomers of various relative length grafted covalently on the underlying electrode. As an important result these ultrathin films retain reversible redox on/off switching and their switching potential can be finely tuned between 0.6 and -0.3 V/SCE despite an overall thickness that remains below 11 nm.

It is now possible to reliably measure single molecule conductance in a wide variety of environments including organic liquids, ultrahigh vacuum, water, ionic liquids, and electrolytes. The most commonly used methods deploy scanning probe microscopes, mechanically formed break junctions, or lithographically formed nanogap contacts. Molecules are generally captured between a pair of facing electrodes, and the junction current response is measured as a function of bias voltage. Gating electrodes can also be added so that the electrostatic potential at the molecular bridge can be independently controlled by this third noncontacting electrode. This can also be achieved in an electrolytic environment using a four-electrode bipotentiostatic configuration, which allows independent electrode potential control of the two contacting electrodes. This is commonly realized using an electrochemical STM and enables single molecule electrical characterization as a function of electrode potential and redox state of the molecular bridge. This has emerged as a powerful tool in modern interfacial electrochemistry and nanoelectrochemistry for studying charge transport across single molecules as a function of electrode potential and the electrolytic environments. Such measurements are possible in electrolytes ranging from aqueous buffers to nonaqueous ionic liquids. In this Account, we illustrate a number of examples of single molecule electrical measurements under electrode potential control use a scanning tunneling microscope (STM) and demonstrate how these can help in the understanding of charge transport in single molecule junctions. Examples showing charge transport following phase coherent tunneling to incoherent charge hopping across redox active molecular bridges are shown. In the case of bipyridinium (or viologen) molecular wires, it is shown how electrochemical reduction leads to an increase of the single molecule conductance, which is controlled by the liquid electrochemical gating. This has been referred to as to a "single molecule transistor configuration" with the gate voltage being provided by the controllable potential achieved through the electrochemical double layer. It is shown how the electrolyte medium can control such gating, with ionic liquids providing more efficient gate coupling than aqueous electrolytes. Control of the conductance of viologen molecular wires can also be achieved by encapsulating the viologen redox moiety within a molecular cage, thereby controlling its immediate environment. Molecular conductance can also be gated through multiple redox states. This has been shown for the redox moiety pyrrolo-tetrathiafulvalene, which undergoes single molecule electrochemical transistor gating through three redox states in molecular junctions. Charge transport through this junction follows a two-step hopping mechanism, demonstrating the role of the redox center in electron transfer across the molecular bridge. Recent electrolyte gating studies of rigid, conjugated redox-active metal complexes with tailored terpyridine coordinating ligands and anchors are also presented. These aforementioned studies have all been performed with gold electrode contacts. The Account concludes with recent data showing that it is now possible to study single molecule electrochemical gating with nickel electrodes. This opens up new perspectives for studying interfacial charge transfer with a wide variety of other electrode materials including semiconductor electrodes and also points toward future opportunities for coupling molecular spintronics and nanoelectrochemistry.

Stochastic behavior becomes an increasingly dominant characteristic of electrochemical systems as we probe them on the smallest scales. Advances in the tools and techniques of nanoelectrochemistry dictate that stochastic phenomena will become more widely manifest in the future. In this Perspective, we outline the conceptual tools that are required to analyze and understand this behavior. We draw on examples from several specific electrochemical systems where important information is encoded in, and can be derived from, apparently random signals. This Perspective attempts to serve as an accessible introduction to understanding stochastic phenomena in electrochemical systems and outlines why they cannot be understood with conventional macroscopic descriptions.

Summary: Sodium ion capacitors (SICs) are designed to deliver both high energy and power densities at low cost. Electric double-layer capacitive cathodes are typically used in these devices, but they lead to very limited capacity. Herein, we apply a pseudocapacitive layered ferric vanadate (Fe-V-O) as cathode to construct non-aqueous SICs with both high energy and power densities. The Fe-V-O nanosheets cathode displays remarkable rate capability and cycling stability. The pseudocapacitive sodium storage mechanism of Fe-V-O, with over 83% of total capacity from capacitive contribution, is confirmed by kinetics analysis and ex situ characterizations. The capacitive-adsorption mechanism of hard carbon (HC) anode is demonstrated, and it delivers excellent rate capability. Based on as-synthesized materials, the assembled HC//Fe-V-O SIC delivers a maximum energy density of 194 Wh kg−1 and power density of 3,942 W kg−1. Our work highlights the advantages of pseudocapacitive cathodes for achieving both high energy and power densities in sodium storage devices. : Electrochemical Energy Storage; Energy Materials; Nanoelectrochemistry Subject Areas: Electrochemical Energy Storage, Energy Materials, Nanoelectrochemistry

The {\pi}-{\pi} interactions between organic molecules are among the most important parameters for optimizing the transport and optical properties of organic transistors, light-emitting diodes, and (bio-) molecular devices. Despite substantial theoretical progress, direct experimental measurement of the {\pi}-{\pi} electronic coupling energy parameter t has remained an old challenge due to molecular structural variability and the large number of parameters that affect the charge transport. Here, we propose a study of {\pi}-{\pi} interactions from electrochemical and current measurements on a large array of ferrocene-thiolated gold nanocrystals. We confirm the theoretical prediction that t can be assessed from a statistical analysis of current histograms. The extracted value of t ca. 35 meV is in the expected range based on our density functional theory analysis. Furthermore, the t distribution is not necessarily Gaussian and could be used as an ultrasensitive technique to assess intermolecular distance fluctuation at the subangstr\"om level. The present work establishes a direct bridge between quantum chemistry, electrochemistry, organic electronics, and mesoscopic physics, all of which were used to discuss results and perspectives in a quantitative manner., Comment: Nano Lett (2017), full text and supporting information

The development of reliable nanosensors offers a number of potential advantages in nanoscale analytical science. A hybrid electron beam-photolithography process was used to fabricate robust and reliable electrochemical nanowire array devices, with highly reproducible critical dimensions, 100 ± 6 nm. Nanowire electrode arrays were designed to permit diffusional independence at each nanowire element in an array thereby maximising limiting currents for optimised electrochemical nanosensing. The electrochemical behaviour of discrete nanowire electrode arrays was investigated using cyclic voltammetry in ferrocenemonocarboxylic acid. Single nanowire devices yielded highly reproducible steady-state sigmoidal waveforms, with typical currents of 179 ± 16 pA. Higher steady-state currents were achieved at nanowire arrays, up to ∼1.2 nA for arrays consisting of six nanowire elements. At low and intermediate scan rates, sigmoidal waveforms were observed for nanowire arrays indicating very fast mass transport. However, voltammetric behaviour consistent with semi-infinite linear diffusion was observed at higher scan rates confirming the presence of overlapping diffusion profiles between neighbouring nanowires within an array. The existence of diffusion overlap between neighbouring nanowire elements was further demonstrated by deviation of measured steady-state currents from estimates, becoming more pronounced with increasing numbers on nanowire elements in the array. Finally capacitive charging of the electrodes was explored, and were found to exhibit very low capacitance typically ∼31 ± 3 nF cm−2 per device, three orders of magnitude less than that reported for conventional microelectrodes (∼20 μF cm−2).

Interference or crosstalk of coexisting redox species results in overlapping of electrochemical signals, and it is a major hurdle in sensor development. In nanogap sensors, redox cycling between two independently biased working electrodes results in an amplified electrochemical signal and an enhanced sensitivity. Here, we report new strategies for selective sensing of three different redox species in a nanogap sensor of a 2 fL volume. Our approach relies on modulating the electrode potentials to define specific potential windows between the two working electrodes; consequently, specific detection of each redox species is achieved. Finite element modeling is employed to simulate the electrochemical processes in the nanogap sensor, and the results are in good agreement with those of experiments.

Recent publications report the direct electrochemical detection of individual enzyme activity via collisions at microelectrodes, though “back of an envelope” calculations challenge the applicability of the experimental method. In light of these studies, we present a comprehensive combined theoretical and computational analysis of the electrode response to a proximate and freely diffusing enzyme generating an electroactive product. We further present experimental data for the enzyme catalase and critically discuss to what extent observed current transients can be unambiguously attributed to single-enzyme collisions by comparison of detection via electrolysis of enzyme reaction products with detection through direct electron transfer reaction mediated via the enzyme.

There is great interest in finding and developing new, efficient, and more active electrocatalytic materials. Surface modification of highly oriented pyrolytic graphite, through the introduction of surface “blisters”, is demonstrated to result in an electrode material with greatly enhanced electrochemical activity. The increased electrochemical activity of these blisters, which are produced by electro-oxidation in HClO4, is revealed through the use of scanning electrochemical cell microscopy (SECCM), coupled with complementary techniques (optical microscopy, field emission-scanning electron microscopy, Raman spectroscopy, and atomic force microscopy). The use of a linear sweep voltammetry (LSV)-SECCM scan regime allows for dynamic electrochemical mapping, where a voltammogram is produced at each pixel, from which movies consisting of spatial electrochemical currents, at a series of applied potentials, are produced. The measurements reveal significantly enhanced electrocatalytic activity at blisters when compared to the basal planes, with a significant cathodic shift in the onset potential of the hydrazine electro-oxidation reaction. The improved electrochemical activity of the hollow structure of blistered graphite could be explained by the increased adsorption of protonated hydrazine at oxygenated defect sites, the ease of ion–solvent intercalation/deintercalation, and the reduced susceptibility to N2 nanobubble attachment (as a product of the reaction). This study highlights the capability of electrochemistry to tailor the surface structure of graphite and presents a new electrocatalyst for hydrazine electro-oxidation.

Interest in nanoparticles has vigorously increased over the last 20 years as more and more studies show how their use can potentially revolutionize science and technology. Their applications span many different academically and industrially relevant fields such as catalysis, materials science, health, etc. Until the past decade, however, nanoparticle studies mostly relied on ensemble studies, thus leaving aside their chemical heterogeneity at the single particle level. Over the past few years, powerful new tools appeared to probe nanoparticles individually and in situ. This Account describes how we drew inspiration from the emerging fields of nanoelectrochemistry and plasmonics-based high resolution holographic microscopy to develop a coupled approach capable of analyzing in operando (electro)chemical reaction over one single nanoparticle. A brief overview of selected optical strategies to image NPs in situ with emphasis on scattering based methods is presented. In an electrochemical context, it is necessary to track particle behavior both in solution and near a polarized electrode, which is why 3D optical observation is particularly appealing. These approaches are discussed together with strategies to track NPs beyond the diffraction limit, allowing a much finer description of their trajectories. Then, the holographic setup is used to study electrochemically triggered Ag NP oxidation reaction in the presence of different electrolytes. Holography is shown to be a powerful technique to track and analyze the trajectory of individual NPs in situ, which further sheds light on in operando behaviors such as electrogenerated NP transport, aggregation, or adsorption. We then show that spectroscopy and scattering-based optical methods are reliable and sensitive to the point of being used to investigate and quantify NP (electro)chemical reactions in model cases. However, since real chemical reactions usually take place in an inherently complex environment, approaches based exclusively on optical imaging only reach their limitations. The strategy is then taken one step further by merging together electrochemical nanoimpact experiments with 3D optical monitoring. Previous strategies are validated by showing that in simple cases, these two independent ways of probing NP size and reactivity yield the same results. For more complicated reactions (e.g., multistep reactions), one must go beyond either technique by showing that the two approaches are perfectly complementary and that the two signals contain information of different natures, thus providing a much better characterization of the reaction. This point is illustrated by studying Ag NP oxidation (single or agglomerates) in the presence of a precipitating agent, where the actual oxidation is uncoupled from the dissolution of the particle, thus proving the point of our symbiotic approach.

The fast-advancing method of nano-impacts is a powerful approach for the immediate detection and characterisation of nanoparticles. During the measurement particles stochastically impact on a biased electrode immersed in a colloidal solution, where they may enable an electrochemical reaction. In the case of a destructive impact, particles electrodissolve at the electrode surface, which can be seen as a spike in the electrode current. While these spikes are successfully used to measure particle concentrations and to determine size distributions via the overall charge transferred per spike, the spike shape is however usually not included in the analysis. In this work, we explore in which ways spike shapes can be exploited to gain additional information on the investigated particle system. To this end, the limiting cases of two reaction models are introduced and discussed in the context of the opportunities and limitations imposed by hardware filters. In particular, we demonstrate that Bessel-type filters conserve the overall charge transferred during an impact event, even if the bandwidth of the signal is far beyond the passband of the filter. Our findings are further compared to experimental data obtained from measurements in aqueous solutions and ionic liquids.

Electrochemical detection of single molecules is being actively pursued as an enabler of new fundamental experiments and sensitive analytical capabilities. Most attempts to date have relied on redox cycling in a nanogap, which consists of two parallel electrodes separated by a nanoscale distance. While these initial experiments have demonstrated single-molecule detection at the proof-of-concept level, several fundamental obstacles need to be overcome to transform the technique into a realistic detection tool suitable for use in more complex settings (e.g., studying enzyme dynamics at single catalytic event level, probing neuronal exocytosis, etc.). In particular, it has become clearer that stochasticity--the hallmark of most single-molecule measurements--can become the key limiting factor on the quality of the information that can be obtained from single-molecule electrochemical assays. Here we employ random-walk simulations to show that this stochasticity is a universal feature of all single-molecule experiments in the diffusively coupled regime and emerges due to the inherent properties of brownian motion. We further investigate the intrinsic coupling between stochasticity and detection capability, paying particular attention to the role of the geometry of the detection device and the finite time resolution of measurement systems. We suggest concrete, realizable experimental modifications and approaches to mitigate these limitations. Overall, our theoretical analyses offer a roadmap for optimizing single-molecule electrochemical experiments, which is not only desirable but also indispensable for their wider employment as experimental tools for electrochemical research and as realistic sensing or detection systems.

Carbonaceous fragments (CF) formed by acid treatment of carbon materials have important properties that are not completely understood. In this work, CF were produced by oxidation of CNT by using mineral acid followed by treatment with NaOH. The role of CF on CNT voltammetric properties was studied by using different materials: oxidized CNT (a-CNT), a-CNT refluxed in NaOH and neutralized with HCl (b-CNT), pristine CNT exposed to a CF suspension (c-CNT), and b-CNT exposed to a CF suspension (r-CNT). The extension of functionalization of these materials was evaluated by thermogravimetric analysis (TGA). The spectroscopic characterization (UV/Vis, fluorescence, FTIR, Raman and NMR) of CF indicates the presence of graphene-type conjugated aromatic rings with highly oxidized moieties. In this work we demonstrate that CF are responsible for the ameliorated voltammetric properties of oxidized CNT. Adsorption of CF on oxidized and non-oxidized CNT showed that CF provide active sites for hydroquinone (HQ) adsorption, enhancing current responses. The interaction of CF with carbon materials depended on both the surface oxidation degree and the surface roughness. Voltammograms from CF adsorbed on oxidized CNT indicate the presence of labile supramolecular structures with a voltammetric response typical of quinoid units. Carbon materials functionalized with CF displayed lower peak potentials and higher currents (30 to 180%) than the unmodified electrodes, demonstrating that CF is a promising material for sensors design., Thanks are due to FCT and COMPETE-QREN-EU for financial support: project PEst-/QUI/UI0686/2013 (Research Centre CQ/UM) and project PEst-C/CTM/ LA0025/2013 (IPC/I3N). RG and EC thank the FCT, POCH, and ESF for his Post- Doc (SFRH/BPD/86690/2012) and her Ph.D. grant (SFRH/BD/87214/2012), respectively., info:eu-repo/semantics/publishedVersion

The development of methods for detecting and manipulating matter at the level of individual macromolecules represents one of the key scientific advancements of recent decades. These techniques allow us to get information that is largely unobtainable otherwise, such as the magnitudes of microscopic forces, mechanistic details of catalytic processes, macromolecular population heterogeneities, and time-resolved, step-by-step observation of complex kinetics. Methods based on optical, mechanical, and ionic-conductance signal transduction are particularly developed. However, there is scope for new approaches that can broaden the range of molecular systems that we can study at this ultimate level of sensitivity and for developing new analytical methods relying on single-molecule detection. Approaches based on purely electrical detection are particularly appealing in the latter context, since they can be easily combined with microelectronics or fluidic devices on a single microchip to create large parallel assays at relatively low cost. A form of electrical signal transduction that has so far remained relatively underdeveloped at the single-molecule level is the direct detection of the charge transferred in electrochemical processes. The reason for this is simple: only a few electrons are transferred per molecule in a typical faradaic reaction, a heterogeneous charge-transfer reaction that occurs at the electrode's surface. Detecting this tiny amount of charge is impossible using conventional electrochemical instrumentation. A workaround is to use redox cycling, in which the charge transferred is amplified by repeatedly reducing and oxidizing analyte molecules as they randomly diffuse between a pair of electrodes. For this process to be sufficiently efficient, the electrodes must be positioned within less than 100 nm of each other, and the analyte must remain between the electrodes long enough for the measurement to take place. Early efforts focused on tip-based nanoelectrodes, descended from scanning electrochemical microscopy, to create suitable geometries. However, it has been challenging to apply these technologies broadly. In this Account, we describe our alternative approach based on electrodes embedded in microfabricated nanochannels, so-called nanogap transducers. Microfabrication techniques grant a high level of reproducibility and control over the geometry of the devices, permitting systematic development and characterization. We have employed these devices to demonstrate single-molecule sensitivity. This method shows good agreement with theoretical analysis based on the Brownian motion of discrete molecules, but only once the finite time resolution of the experimental apparatus is taken into account. These results highlight both the random nature of single-molecule signals and the complications that it can introduce in data interpretation. We conclude this Account with a discussion on how scientists can overcome this limitation in the future to create a new experimental platform that can be generally useful for both fundamental studies and analytical applications.

A new type of electrochemical cell has been developed for use in electrochemical, chemical and biological applications. Using a platinum microelectrode as working electrode, this cell incorporates a silver microelectrode as reference electrode. These microelectrodes, whose area is equal to 1 μm 2 , were fabricated using photolithography, sputtering, and focused ion beam (FIB) technologies since these micro-fabrication techniques allow us to develop miniaturized electrochemical cells useful either for nanoelectrochemistry or biosensors applications. In this study, we show it is possible to coat a surface by chemical or biological compounds by immersing the microelectrodes in a solution, then setting a difference of potential between the two microelectrodes of the cell. For example, we used this miniaturized cell to realize the electrochemical polymerization of aniline into polyaniline to show that this electrochemical cell is efficient to coat a surface with a thin film of polymer.

Nanoelectrochemistry is an important and growing branch of electrochemistry that encompasses a number of key research areas, including (electro)catalysis, energy storage, biomedical/environmental sensing, and electrochemical imaging. Nanoscale electrochemical measurements are often performed in confined environments over prolonged experimental time scales with nonisolated quasi-reference counter electrodes (QRCEs) in a simplified two-electrode format. Herein, we consider the stability of commonly used Ag/AgCl QRCEs, comprising an AgCl-coated wire, in a nanopipet configuration, which simulates the confined electrochemical cell arrangement commonly encountered in nanoelectrochemical systems. Ag/AgCl QRCEs possess a very stable reference potential even when used immediately after preparation and, when deployed in Cl– free electrolyte media (e.g., 0.1 M HClO4) in the scanning ion conductance microscopy (SICM) format, drift by only ca. 1 mV h–1 on the several hours time scale. Furthermore, contrary to some previous reports, when employed in a scanning electrochemical cell microscopy (SECCM) format (meniscus contact with a working electrode surface), Ag/AgCl QRCEs do not cause fouling of the surface (i.e., with soluble redox byproducts, such as Ag+) on at least the 6 h time scale, as long as suitable precautions with respect to electrode handling and placement within the nanopipet are observed. These experimental observations are validated through finite element method (FEM) simulations, which consider Ag+ transport within a nanopipet probe in the SECCM and SICM configurations. These results confirm that Ag/AgCl is a stable and robust QRCE in confined electrochemical environments, such as in nanopipets used in SICM, for nanopore measurements, for printing and patterning, and in SECCM, justifying the widespread use of this electrode in the field of nanoelectrochemistry and beyond.\ud \ud