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Transition metal (oxy)hydroxides are promising electrocatalysts for the oxygen evolution reaction1-3. The properties of these materials evolve dynamically and heterogeneously4 with applied voltage through ion insertion redox reactions, converting materials that are inactive under open circuit conditions into active electrocatalysts during operation5. The catalytic state is thus inherently far from equilibrium, which complicates its direct observation. Here, using a suite of correlative operando scanning probe and X-ray microscopy techniques, we establish a link between the oxygen evolution activity and the local operational chemical, physical and electronic nanoscale structure of single-crystalline ß-Co(OH)2 platelet particles. At pre-catalytic voltages, the particles swell to form an α-CoO2H1.5·0.5H2O-like structure-produced through hydroxide intercalation-in which the oxidation state of cobalt is +2.5. Upon increasing the voltage to drive oxygen evolution, interlayer water and protons de-intercalate to form contracted ß-CoOOH particles that contain Co3+ species. Although these transformations manifest heterogeneously through the bulk of the particles, the electrochemical current is primarily restricted to their edge facets. The observed Tafel behaviour is correlated with the local concentration of Co3+ at these reactive edge sites, demonstrating the link between bulk ion-insertion and surface catalytic activity.
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Silver nanoparticles (AgNPs) conjugated with polymers are well-known for their powerful and effective antimicrobial properties. In particular, the incorporation of AgNPs in biocompatible catecholamine-based polymers, such as polydopamine (PDA), has recently shown promising antimicrobial activity, due to the synergistic effects of the AgNPs, silver(I) ions released and PDA. In this study, we generated AgNPs-PDA-patterned surfaces by localised electrochemical depositions, using a double potentiostatic method via scanning electrochemical cell microscopy (SECCM). This technique enabled the assessment of a wide parameter space in a high-throughput manner. The optimised electrodeposition process resulted in stable and homogeneously distributed AgNP-microspots, and their antimicrobial activity against Escherichia coli was assessed using atomic force microscopy (AFM)-based force spectroscopy, in terms of bacterial adhesion and cell elasticity. We observed that the bacterial outer membrane underwent significant structural changes, when in close proximity to the AgNPs, namely increased hydrophilicity and stiffness loss. The spatially varied antimicrobial effect found experimentally was rationalised by numerical simulations of silver(I) concentration profiles.
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Escherichia coli , Nanopartículas Metálicas , Prata , Prata/química , Prata/farmacologia , Nanopartículas Metálicas/química , Escherichia coli/efeitos dos fármacos , Antibacterianos/farmacologia , Antibacterianos/química , Microscopia de Força Atômica , Polímeros/química , Polímeros/farmacologia , Aderência Bacteriana/efeitos dos fármacos , Indóis/química , Indóis/farmacologiaRESUMO
Understanding the solid electrolyte interphase (SEI) formation and (de)lithiation phenomena at silicon (Si) electrodes is key to improving the performance and lifetime of Si-based lithium-ion batteries. However, these processes remain somewhat elusive, and, in particular, the role of Si surface termination merits further consideration. Here, scanning electrochemical cell microscopy (SECCM) is used in a glovebox, followed by secondary ion mass spectrometry (SIMS) at identical locations to study the local electrochemical behavior and associated SEI formation, comparing Si (100) with a native oxide layer (SiOx /Si) and etched with hydrofluoric acid (HF-Si). HF-Si shows greater spatial electrochemical heterogeneity and inferior lithiation reversibility than SiOx /Si. This is attributed to a weakly passivating SEI and irreversible lithium trapping at the Si surface. Combinatorial screening of charge/discharge cycling by SECCM with co-located SIMS reveals SEI chemistry as a function of depth. While the SEI thickness is relatively independent of the cycle number, the chemistry - particularly in the intermediate layers - depends on the number of cycles, revealing the SEI to be dynamic during cycling. This work serves as a foundation for the use of correlative SECCM/SIMS as a powerful approach to gain fundamental insights on complex battery processes at the nano- and microscales.
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ConspectusElectrochemical reduction of the greenhouse gas CO2 offers prospects for the sustainable generation of fuels and industrially useful chemicals when powered by renewable electricity. However, this electrochemical process requires the use of highly stable, selective, and active catalysts. The development of such catalysts should be based on a detailed kinetic and mechanistic understanding of the electrochemical CO2 reduction reaction (eCO2RR), ideally through the resolution of active catalytic sites in both time (i.e., temporally) and space (i.e., spatially). In this Account, we highlight two advanced spatiotemporal voltammetric techniques for electrocatalytic studies and describe the considerable insights they provide on the eCO2RR. First, Fourier transformed large-amplitude alternating current voltammetry (FT ac voltammetry), as applied by the Monash Electrochemistry Group, enables the resolution of rapid underlying electron-transfer processes in complex reactions, free from competing processes, such as the background double-layer charging current, slow catalytic reactions, and solvent/electrolyte electrolysis, which often mask conventional voltammetric measurements of the eCO2RR. Crucially, FT ac voltammetry allows details of the catalytically active sites or the rate-determining step to be revealed under catalytic turnover conditions. This is well illustrated in investigations of the eCO2RR catalyzed by Bi where formate is the main product. Second, developments in scanning electrochemical cell microscopy (SECCM) by the Warwick Electrochemistry and Interfaces Group provide powerful methods for obtaining high-resolution activity maps and potentiodynamic movies of the heterogeneous surface of a catalyst. For example, by coupling SECCM data with colocated microscopy from electron backscatter diffraction (EBSD) or atomic force microscopy, it is possible to develop compelling correlations of (precatalyst) structure-activity at the nanoscale level. This correlative electrochemical multimicroscopy strategy allows the catalytically more active region of a catalyst, such as the edge plane of two-dimensional materials and the grain boundaries between facets in a polycrystalline metal, to be highlighted. The attributes of SECCM-EBSD are well-illustrated by detailed studies of the eCO2RR on polycrystalline gold, where carbon monoxide is the main product. Comparing SECCM maps and movies with EBSD images of the same region reveals unambiguously that the eCO2RR is enhanced at surface-terminating dislocations, which accumulate at grain boundaries and slip bands. Both FT ac voltammetry and SECCM techniques greatly enhance our understanding of the eCO2RR, significantly boosting the electrochemical toolbox and the information available for the development and testing of theoretical models and rational catalyst design. In the future, it may be possible to further enhance insights provided by both techniques through their integration with in situ and in operando spectroscopy and microscopy methods.
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Anatase TiO2 is a promising material for Li-ion (Li+ ) batteries with fast charging capability. However, Li+ (de)intercalation dynamics in TiO2 remain elusive and reported diffusivities span many orders of magnitude. Here, we develop a smart protocol for scanning electrochemical cell microscopy (SECCM) with in situ optical microscopy (OM) to enable the high-throughput charge/discharge analysis of single TiO2 nanoparticle clusters. Directly probing active nanoparticles revealed that TiO2 with a size of ≈50â nm can store over 30 % of the theoretical capacity at an extremely fast charge/discharge rate of ≈100â C. This finding of fast Li+ storage in TiO2 particles strengthens its potential for fast-charging batteries. More generally, smart SECCM-OM should find wide applications for high-throughput electrochemical screening of nanostructured materials.
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Indium tin oxide (ITO) is a popular electrode choice, with diverse applications in (photo)electrocatalysis, organic photovoltaics, spectroelectrochemistry and sensing, and as a support for cell biology studies. Although ITO surfaces exhibit heterogeneous local electrical conductivity, little is known as to how this translates to electrochemistry at the same scale. This work investigates nanoscale electrochemistry at ITO electrodes using high-resolution scanning electrochemical cell microscopy (SECCM). The nominally fast outer-sphere one-electron oxidation of 1,1'-ferrocenedimethanol (FcDM) is used as an electron transfer (ET) kinetic marker to reveal the charge transfer properties of the ITO/electrolyte interface. SECCM measures spatially resolved linear sweep voltammetry at an array of points across the ITO surface, with the topography measured synchronously. Presentation of SECCM data as current maps as a function of potential reveals that, while the entire surface of ITO is electroactive, the ET activity is highly spatially heterogeneous. Kinetic parameters (standard rate constant, k0, and transfer coefficient, α) for FcDM0/+ are assigned from 7200 measurements at sites across the ITO surface using finite element method modeling. Differences of 3 orders of magnitude in k0 are revealed, and the average k0 is about 20 times larger than that measured at the macroscale. This is attributed to macroscale ET being largely limited by lateral conductivity of the ITO electrode under electrochemical operation, rather than ET kinetics at the ITO/electrolyte interface, as measured by SECCM. This study further demonstrates the considerable power of SECCM for direct nanoscale characterization of electrochemical processes at complex electrode surfaces.
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Compostos de Estanho , Eletroquímica , Eletrodos , Oxirredução , Compostos de Estanho/químicaRESUMO
Understanding how the bulk structure of a material affects catalysis on its surface is critical to the development of actionable catalyst design principles. Bulk defects have been shown to affect electrocatalytic materials that are important for energy conversion systems, but the structural origins of these effects have not been fully elucidated. Here we use a combination of high-resolution scanning electrochemical cell microscopy and electron backscatter diffraction to visualize the potential-dependent electrocatalytic carbon dioxide [Formula: see text] electroreduction and hydrogen [Formula: see text] evolution activity on Au electrodes and probe the effects of bulk defects. Comparing colocated activity maps and videos to the underlying microstructure and lattice deformation supports a model in which CO2 electroreduction is selectively enhanced by surface-terminating dislocations, which can accumulate at grain boundaries and slip bands. Our results suggest that the deliberate introduction of dislocations into materials is a promising strategy for improving catalytic properties.
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The aim of this paper is to describe the scientific journey taken to arrive at present-day nanoelectrochemistry and consider how the area might develop in the future, particularly in light of papers presented at this Faraday Discussion. By adopting a generational approach, this brief contribution traces the story of the nanoelectrochemistry family within the broader electrochemistry field, with a focus on scientific capability and themes that were important to each generation. I shall consider research questions and the impact of technology that was developed or available in each period. Nanoelectrochemistry is still somewhat niche, but is attracting increasing numbers of researchers. It is set to become a major part of electrochemistry and interfacial science. It is studied by people with a fairly unique skillset, and I shall speculate on the skills and expertise that will be needed by nanoelectrochemists to address the challenges and opportunities that lie ahead. I conclude by asking: who will be the nanoelectrochemists of the future and what will they do?
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Eletroquímica , HumanosRESUMO
We describe the combination of scanning electrochemical cell microscopy (SECCM) and interference reflection microscopy (IRM) to produce a compelling technique for the study of interfacial processes and to track the SECCM meniscus status in real-time. SECCM allows reactions to be confined to well defined nm-to-µm-sized regions of a surface, and for experiments to be repeated quickly and easily at multiple locations. IRM is a highly surface-sensitive technique which reveals processes happening (very) close to a substrate with temporal and spatial resolution commensurate with typical electrochemical techniques. By using thin transparent conductive layers on glass as substrates, IRM can be coupled to SECCM, to allow real-time in situ optical monitoring of the SECCM meniscus and of processes that occur within it at the electrode/electrolyte interface. We first use the technique to assess the stability of the SECCM meniscus during voltammetry at an indium tin oxide (ITO) electrode at close to neutral pH, demonstrating that the meniscus contact area is rather stable over a large potential window and reproducible, varying by only ca. 5% over different SECCM approaches. At high cathodic potentials, subtle electrowetting is easily detected and quantified. We also look inside the meniscus to reveal surface changes at extreme cathodic potentials, assigned to the possible formation of indium nanoparticles. Finally, we examine the effect of meniscus size and driving potential on CaCO3 precipitation at the ITO electrode as a result of electrochemically-generated pH swings. We are able to track the number, spatial distribution and morphology of material with high spatiotemporal resolution and rationalise some of the observed deposition patterns with finite element method modelling of reactive-transport. Growth of solid phases on surfaces from solution is an important pathway to functional materials and SECCM-IRM provides a means for in situ or in operando visualisation and tracking of these processes with improved fidelity. We anticipate that this technique will be particularly powerful for the study of phase formation processes, especially as the high throughput nature of SECCM-IRM (where each spot is a separate experiment) will allow for the creation of large datasets, exploring a wide experimental parameter landscape.
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Revealing how formation protocols influence the properties of the solid-electrolyte interphase (SEI) on Si electrodes is key to developing the next generation of Li-ion batteries. SEI understanding is, however, limited by the low-throughput nature of conventional characterisation techniques. Herein, correlative scanning electrochemical cell microscopy (SECCM) and shell-isolated nanoparticles for enhanced Raman spectroscopy (SHINERS) are used for combinatorial screening of the SEI formation under a broad experimental space (20 sets of different conditions with several repeats). This novel approach reveals the heterogeneous nature and dynamics of the SEI electrochemical properties and chemical composition on Si electrodes, which evolve in a characteristic manner as a function of cycle number. Correlative SECCM/SHINERS has the potential to screen thousands of candidate experiments on a variety of battery materials to accelerate the optimization of SEI formation methods, a key bottleneck in battery manufacturing.
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Nanopipettes are finding increasing use as nano "test tubes", with reactions triggered through application of an electrochemical potential between electrodes in the nanopipette and a bathing solution (bath). Key to this application is an understanding of how the applied potential induces mixing of the reagents from the nanopipette and the bath. Here, we demonstrate a laser scanning confocal microscope (LSCM) approach to tracking the ingress of dye into a nanopipette (20-50 nm diameter end opening). We examine the case of dianionic fluorescein under alkaline conditions (pH 11) and large applied tip potentials (±10 V), with respect to the bath, and surprisingly find that dye ingress from the bath into the nanopipette is not observed under either sign of potential. Finite element method (FEM) simulations indicate this is due to the dominance of electro-osmosis in mass transport, with electro-osmotic flow in the conventional direction at +10 V and electro-osmosis of the second kind acting in the same direction at -10 V, caused by the formation of significant space charge in the center of the orifice. The results highlight the significant deviation in mass transport behavior that emerges at the nanoscale and the utility of the combined LSCM and FEM approach in deepening understanding, which in turn should promote new applications of nanopipettes.
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Microscopia Confocal , OsmoseRESUMO
Scanning ion conductance microscopy (SICM) is a powerful and versatile technique that allows an increasingly wide range of interfacial properties and processes to be studied. SICM employs a nanopipette tip that contains electrolyte solution and a quasi-reference counter electrode (QRCE), to which a potential is applied with respect to a QRCE in a bathing solution, in which the tip is placed. The work herein considers the potential-controlled delivery of uncharged electroactive molecules (solute) from an SICM tip to a working electrode substrate to determine the effect of the substrate on electroosmotic flow (EOF). Specifically, the local delivery of hydroquinone from the tip to a carbon fiber ultramicroelectrode (CF UME) provides a means of quantifying the rate of mass transport from the nanopipette and mapping electroactivity via the CF UME current response for hydroquinone oxidation to benzoquinone. EOF, and therefore species delivery, has a particularly strong dependence on the charge of the substrate surface at close nanopipette-substrate surface separations, with implications for retaining neutral solute within the tip predelivery and for the delivery process itself, both controlled via the applied tip potential. Finite element method (FEM) simulations of mass transport and reactivity are used to explain the experimental observations and identify the nature of EOF, including unusual flow patterns under certain conditions. The combination of experimental results with FEM simulations provides new insights on mass transport in SICM that will enhance quantitative applications and enable new possibilities for the use of nanopipettes for local delivery.
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Eletro-Osmose , Microscopia , Eletrodos , Íons , CintilografiaRESUMO
Cobaloximes are promising, earth-abundant catalysts for the light-driven hydrogen evolution reaction (HER). Typically, these cobalt(III) complexes are prepared inâ situ or employed in their neutral form, for example, [Co(dmgH)2 (py)Cl], even though related complex salts have been reported previously and could, in principle, offer improved catalytic activity as well as more efficient immobilization on solid support. Herein, we report an interdisciplinary investigation into complex salts [Co(dmgH)2 (py)2 ]+ [Co(dmgBPh2 )2 Cl2 ]- , TBA + [ Co ( dmgBPh 2 ) 2 Cl 2 ] - and [Co(dmgH)2 (py)2 ]+ BArF- . We describe their strategic syntheses from the commercially available complex [Co(dmgH)2 (py)Cl] and demonstrate that these double and single complex salts are potent catalysts for the light-driven HER. We also show that scanning electrochemical cell microscopy can be used to deposit arrays of catalysts [Co(dmgH)2 (py)2 ]+ [Co(dmgBPh2 )2 Cl2 ]- , TBA + [ Co ( dmgBPh 2 ) 2 Cl 2 ] - and [Co(dmgH)2 (py)Cl] on supported and free-standing amino-terminated â¼1-nm-thick carbon nanomembranes (CNMs). Photocatalytic H2 evolution at such arrays was quantified with Pd microsensors by scanning electrochemical microscopy, thus providing a new approach for catalytic evaluation and opening up novel routes for the creation and analysis of "designer catalyst arrays", nanoprinted in a desired pattern on a solid support.
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Many applications in modern electrochemistry, notably electrosynthesis and energy storage/conversion take advantage of the "tunable" physicochemical properties (e.g., proton availability and/or electrochemical stability) of nonaqueous (e.g., aprotic) electrolyte media. This work develops general guidelines pertaining to the use of scanning electrochemical cell microscopy (SECCM) in aprotic solvent electrolyte media to address contemporary structure-electrochemical activity problems. Using the simple outer-sphere Fc0/+ process (Fc = ferrocene) as a model system, high boiling point (low vapor pressure) solvents give rise to highly robust and reproducible electrochemistry, whereas volatile (low boiling point) solvents need to be mixed with suitable low melting point supporting electrolytes (e.g., ionic liquids) or high boiling point solvents to avoid complications associated with salt precipitation/crystallization on the scanning (minutes to hours) time scale. When applied to perform microfabrication-specifically the electrosynthesis of the conductive polymer, polypyrrole-the optimized SECCM set up produces highly reproducible arrays of synthesized (electrodeposited) material on a commensurate scale to the employed pipet probe. Applying SECCM to map electrocatalytic activity-specifically the electro-oxidation of iodide at polycrystalline platinum-reveals unique (i.e., structure-dependent) patterns of surface activity, with grains of specific crystallographic orientation, grain boundaries and areas of high local surface misorientation identified as potential electrocatalytic "hot spots". The work herein further cements SECCM as a premier technique for structure-function-activity studies in (electro)materials science and will open up exciting new possibilities through the use of aprotic solvents for rational analysis/design in electrosynthesis, microfabrication, electrochemical energy storage/conversion, and beyond.
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This paper reports on the use of scanning ion conductance microscopy (SICM) to locally map the ionic properties and charge environment of two live bacterial strains: the Gram-negative Escherichia coli and the Gram-positive Bacillus subtilis. SICM results find heterogeneities across the bacterial surface and significant differences among the Gram-positive and Gram-negative bacteria. The bioelectrical environment of the B. subtilis was found to be considerably more negatively charged compared to E. coli. SICM measurements, fitted to a simplified finite element method (FEM) model, revealed surface charge values of -80 to -140 mC m-2 for the Gram-negative E. coli. The Gram-positive B. subtilis show a much higher conductivity around the cell wall, and surface charge values between -350 and -450 mC m-2 were found using the same simplified model. SICM was also able to detect regions of high negative charge near B. subtilis, not detected in the topographical SICM response and attributed to the extracellular polymeric substance. To further explore how the B. subtilis cell wall structure can influence the SICM current response, a more comprehensive FEM model, accounting for the physical properties of the Gram-positive cell wall, was developed. The new model provides a more realistic description of the cell wall and allows investigation of the relation between its key properties and SICM currents, building foundations to further investigate and improve understanding of the Gram-positive cellular microenvironment.
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Bacillus/citologia , Escherichia coli/citologia , Análise de Elementos Finitos , Microscopia , Bacillus/metabolismo , Parede Celular/metabolismo , Microambiente Celular , Escherichia coli/metabolismoRESUMO
Electrochemical impedance spectroscopy (EIS) is a versatile tool for electrochemistry, particularly when applied locally to reveal the properties and dynamics of heterogeneous interfaces. A new method to generate local electrochemical impedance spectra is outlined, by applying a harmonic bias between a quasi-reference counter electrode (QRCE) placed in a nanopipet tip of a scanning ion conductance microscope (SICM) and a conductive (working electrode) substrate (two-electrode setup). The AC frequency can be tuned so that the magnitude of the impedance is sensitive to the tip-to-substrate distance, whereas the phase angle is broadly defined by the local capacitive response of the electrical double layer (EDL) of the working electrode. This development enables the surface topography and the local capacitance to be sensed reliably, and separately, in a single measurement. Further, self-referencing the probe impedance near the surface to that in the bulk solution allows the local capacitive response of the working electrode substrate in the overall AC signal to be determined, establishing a quantitative footing for the methodology. The spatial resolution of AC-SICM is an order of magnitude larger than the tip size (100 nm radius), for the studies herein, due to frequency dispersion. Comprehensive finite element method (FEM) modeling is undertaken to optimize the experimental conditions and minimize the experimental artifacts originating from the frequency dispersion phenomenon, and provides an avenue to explore the means by which the spatial resolution could be further improved.
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Calcium carbonate (CaCO3) is one of the most well-studied and abundant natural materials on Earth. Crystallisation of CaCO3 is often observed to proceed via an amorphous calcium carbonate (ACC) phase, as a precursor to more stable crystalline polymorphs such as vaterite and calcite. Despite its importance, the kinetics of ACC formation have proved difficult to study, in part due to rapid precipitation at moderate supersaturations, and the instability of ACC with respect to all other polymorphs. However, ACC can be stabilised under confinement conditions, such as those provided by a nanopipette. This paper demonstrates electrochemical mixing of a Ca2+ salt (CaCl2) and a HCO3- salt (NaHCO3) in a nanopipette to repeatedly and reversibly precipitate nanoparticles of ACC under confined conditions, as confirmed by scanning transmission electron microscopy (STEM). Measuring the current as a function of applied potential across the end of the nanopipette and time provides millisecond-resolved measurements of the induction time for ACC precipitation. We demonstrate that under conditions of electrochemical mixing, ACC precipitation is extremely fast, and highly pH sensitive with an apparent third order dependence on CO32- concentration. Furthermore, the rate is very similar for the equivalent CO32- concentrations in D2O, suggesting that neither ion dehydration nor HCO3- deprotonation represent significant energetic barriers to the formation of ACC. Finite element method simulations of the electrochemical mixing process enable the supersaturation to be estimated for all conditions and accurately predict the location of precipitation.
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Achieving control over the size distribution of metal-organic-framework (MOF) nanoparticles is key to biomedical applications and seeding techniques. Electrochemical control over the nanoparticle synthesis of the MOF, HKUST-1, is achieved using a nanopipette injection method to locally mix Cu2+ salt precursor and benzene-1,3,5-tricarboxylate (BTC3- ) ligand reagents, to form MOF nanocrystals, and collect and characterise them on a TEM grid. Inâ situ analysis of the size and translocation frequency of HKUST-1 nanoparticles is demonstrated, using the nanopipette to detect resistive pulses as nanoparticles form. Complementary modelling of mass transport in the electric field, enables particle size to be estimated and explains the feasibility of particular reaction conditions, including inhibitory effects of excess BTC3- . These new methods should be applicable to a variety of MOFs, and scaling up synthesis possible via arrays of nanoscale reaction centres, for example using nanopore membranes.
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Nanostructured electrochemical interfaces (electrodes) are found in diverse applications ranging from electrocatalysis and energy storage to biomedical and environmental sensing. These functional materials, which possess compositional and structural heterogeneity over a wide range of length scales, are usually characterized by classical macroscopic or "bulk" electrochemical techniques that are not well-suited to analyzing the nonuniform fluxes that govern the electrochemical response at complex interfaces. In this Perspective, we highlight new directions to studying fundamental electrochemical and electrocatalytic phenomena, whereby nanoscale-resolved information on activity is related to electrode structure and properties colocated and at a commensurate scale by using complementary high-resolution microscopy techniques. This correlative electrochemical multimicroscopy strategy aims to unambiguously resolve structure and activity by identifying and characterizing the structural features that constitute an active surface, ultimately facilitating the rational design of functional electromaterials. The discussion encompasses high-resolution correlative structure-activity investigations at well-defined surfaces such as metal single crystals and layered materials, extended structurally/compositionally heterogeneous surfaces such as polycrystalline metals, and ensemble-type electrodes exemplified by nanoparticles on an electrode support surface. This Perspective provides a roadmap for next-generation studies in electrochemistry and electrocatalysis, advocating that complex electrode surfaces and interfaces be broken down and studied as a set of simpler "single entities" (e.g., steps, terraces, defects, crystal facets, grain boundaries, single particles), from which the resulting nanoscale understanding of reactivity can be used to create rational models, underpinned by theory and surface physics, that are self-consistent across broader length scales and time scales.
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Scanning ion conductance microscopy (SICM) is becoming a powerful multifunctional tool for probing and analyzing surfaces and interfaces. This work outlines methodology for the quantitative controlled delivery of ionic redox-active molecules from a nanopipette to a substrate electrode, with a high degree of spatial and temporal precision. Through control of the SICM bias applied between a quasi-reference counter electrode (QRCE) in the SICM nanopipette probe and a similar electrode in bulk solution, it is shown that ionic redox species can be held inside the nanopipette, and then pulse-delivered to a defined region of a substrate positioned beneath the nanopipette. A self-referencing hopping mode imaging protocol is implemented, where reagent is released in bulk solution (reference measurement) and near the substrate surface at each pixel in an image, with the tip and substrate currents measured throughout. Analysis of the tip and substrate current data provides an improved understanding of mass transport and nanoscale delivery in SICM and a new means of synchronously mapping electrode reactivity, surface topography, and charge. Experiments on Ru(NH3)63+ reduction to Ru(NH3)62+ and dopamine oxidation in aqueous solution at a carbon fiber ultramicroelectrode (UME), used as the substrate, illustrate these aspects. Finite element method (FEM) modeling provides quantitative understanding of molecular delivery in SICM. The approach outlined constitutes a new methodology for electrode mapping and provides improved insights on the use of SICM for controlled delivery to interfaces generally.