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Understanding the oxidation/reduction dynamics of secondary microparticles formed from agglomerated nanoscale primary particles is crucial for advancing electrochemical energy storage technologies. In this study, the behavior of individual copper hexacyanoferrate (CuHCF) microparticles is explored at both global and local scales combining scanning electrochemical microscopy (SECM), for electrochemical interrogation of a single, but global-scale microparticle, and optical microscopy monitoring to obtain a higher resolution dynamic image of the local electrochemistry within the same particle. Chronoamperometric experiments unveil a multistep oxidation/reduction process with varying dynamics. On the one hand, the global SECM analysis enables quantifying the charge transfer as well as its dynamics at the single microparticle level during the oxidation/reduction cycles by a redox mediator in solution. These conditions allow mimicking the charge storage processes in these particles when they are used as solid boosters in redox flow batteries. On the other hand, optical imaging with sub-particle resolution allows the mapping of local conversion rates and state-of-charge within individual CuHCF particles. These maps reveal that regions of different material loadings exhibit varying charge storage capacities and conversion rates. The findings highlight the significance of porous nanostructures and provide valuable insights for designing more efficient energy storage materials.
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Tip-enhanced Raman spectroscopy (TERS) is an emerging nanospectroscopy technique whose implementation in situ/operando, namely, in the liquid phase and under electrochemical polarization (EC-TERS), remains challenging. The investigation of electrochemical processes at the nanoscale, in real time and over wide potential windows can be of particular interest but tedious when using EC-STM-TERS. This approach was successfully applied to the investigation of a well-established but yet complex system (a thiolated nitrobenzene derivative 4-NBM) whose reduction mechanism involves various multistep reaction paths, most likely pH-dependent. In light of the EC-TERS analysis carried out under specific conditions limiting the full (6 e-/6 H+) electrochemical reduction of 4-NBM and its photocoupling, a bimolecular electrochemical reaction path, difficult to evidence from the electrochemical response only, is proposed.
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The stark difference between global and local metal oxidation dynamics underscores the need for methodologies capable of performing precise sub-µm-scale and wide-field measurements. In this study, we present reflective microscopy as a tool developed to address this challenge, illustrated by the example of chronoamperometric Fe oxidation in a NaCl solution. Analysis at a local scale of 10 s of µm has revealed three distinct periods of Fe oxidation: the initial covering of the metal interface with a surface film, followed by the electrochemical conversion of the formed surface film, and finally, the in-depth oxidation of Fe. In addition, thermodynamic calculations and the quantitative analysis of changes in optical signal (light intensity), correlated with variations in refractive indexes, suggest the initial formation of maghemite, followed by its subsequent conversion to magnetite. The reactivity maps for all three periods are heterogeneous, which can be attributed to the preferential oxidation of certain crystallographic grains. Notably, at the global scale of 100 s of µm, reactivity initiates at the electrode border and progresses toward its center, demonstrating a unique pattern that is independent of the local metal structure. This finding underscores the significance of simultaneously employing sub-µm-precise, quantitative, and wide-field measurements for a comprehensive description of metal oxidation processes.
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We explore the possibility of coupling the transport of ions and water in a nanochannel with the chemical transformation of a reactant at an individual catalytic nanoparticle (NP). Such configuration could be interesting for constructing artificial photosynthesis devices coupling the asymmetric production of ions at the catalytic NP, with the ion selectivity of the nanochannels acting as ion pumps. Herein we propose to observe how such ion pumping can be coupled to an electrochemical reaction operated at the level of an individual electrocatalytic Pt NP. This is achieved by confining a (reservoir) droplet of electrolyte to within a few micrometres away from an electrocatalytic Pt NP on an electrode. While the region of the electrode confined by the reservoir and the NP are cathodically polarised, operando optical microscopy reveals the growth of an electrolyte nanodroplet on top of the NP. This suggests that the electrocatalysis of the oxygen reduction reaction operates at the NP and that an electrolyte nanochannel is formed - acting as an ion pump - between the reservoir and the NP. We have described here the optically imaged phenomena and their relevance to the characterization of the electrolyte nanochannel linking the NPs to the electrolyte microreservoir. Additionally, we have addressed the capacity of the nanochannel to transport ions and solvent flow to the NP.
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Gas nanobubbles are directly linked to many important chemical reactions. While they can be detrimental to operational devices, they also reflect the local activity at the nanoscale. Here, supercrystals made of highly monodisperse Ag@Pt core-shell nanoparticles are first grown onto a solid support and fully characterized by electron microscopies and X-ray scattering. Supercrystals are then used as a plasmonic photocatalytic platform for triggering the hydrogen evolution reaction. The catalytic activity is measured operando at the single supercrystal level by high-resolution optical microscopy, which allows gas nanobubble nucleation to be probed at the early stage with high temporal resolution and the amount of gas molecules trapped inside them to be quantified. Finally, a correlative microscopy approach and high-resolution electron energy loss spectroscopy help to decipher the mechanisms at the origin of the local degradation of the supercrystals during catalysis, namely nanoscale erosion and corrosion.
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This work proposes a novel method for measuring the intrinsic activity of single metal-based nanoparticles towards water reduction in neutral media at industrially relevant current densities. Instead of using gas nanobubbles as proxy, the method uses optical microscopy to track the local footprint of the reaction through the precipitation of metal hydroxide, which is associated to the local pH increase during electrocatalysis. The results show the electrocatalytic activities of different types of metal nanoparticles and bifunctionnal core-shell nanostructures made of Ni and Pt, and demonstrate the importance of metal hydroxide nano-shells in enhancing electrocatalysis. This method should be generalizable to any electrocatalytic reaction involving pH changes such as nitrate or CO2 reduction.
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We report the experimental reassessment of the widely admitted concerted reduction mechanism for diazonium electroreduction. Ultrafast cyclic voltammetry was exploited to demonstrate the existence of a stepwise pathway, and real-time spectroelectrochemistry experiments allowed visualization of the spectral signature of an evolution product of the phenyldiazenyl radical intermediate. Unambiguous identification of the diazenyl species was achieved by radical trapping followed by X-ray structure resolution. The electrochemical generation of this transient under intermediate energetic conditions calls into question our comprehension of the layer structuration when surface modification is achieved via the diazonium electrografting technique as this azo-containing intermediate could be responsible for the systematic presence of azo bridges in nanometric films.
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Monitoring chemical reactions in solutions at the scale of individual entities is challenging: single-particle detection requires small confocal volumes, which are hardly compatible with Brownian motion, particularly when long integration times are necessary. Here, we propose a real-time (10 Hz) holography-based nm-precision 3D tracking of single moving nanoparticles. Using this localization, the confocal collection volume is dynamically adjusted to follow the moving nanoparticle and allow continuous spectroscopic monitoring. This concept is applied to study galvanic exchange in freely moving colloidal silver nanoparticles with gold ions generated in situ. While the Brownian trajectory reveals particle size, spectral shifts dynamically reveal composition changes and transformation kinetics at the single-object level, pointing at different transformation kinetics for free and tethered particles.
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The nanostructuration of an electrochemical interface dictates its micro- and macroscopic behavior. It is generally highly complex and often evolves under operating conditions. Electrochemistry at these nanostructurations can be imaged both operando and/or ex situ at the single nanoobject or nanoparticle (NP) level by diverse optical, electron, and local probe microscopy techniques. However, they only probe a tiny random fraction of interfaces that are by essence highly heterogeneous. Given the above background, correlative multimicroscopy strategy coupled to electrochemistry in a droplet cell provides a unique solution to gain mechanistic insights in electrocatalysis. To do so, a general machine-vision methodology is depicted enabling the automated local identification of various physical and chemical descriptors of NPs (size, composition, activity) obtained from multiple complementary operando and ex situ microscopy imaging of the electrode. These multifarious microscopically probed descriptors for each and all individual NPs are used to reconstruct the global electrochemical response. Herein the methodology unveils the competing processes involved in the electrocatalysis of hydrogen evolution reaction at nickel based NPs, showing that Ni metal activity is comparable to that of platinum.
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Nanopartículas del Metal , Platino (Metal) , Hidrógeno , Nanopartículas del Metal/química , Microscopía/métodos , Níquel/química , Platino (Metal)/químicaRESUMEN
The fast establishment of structure-reactivity relationships is crucial to identifying the most appropriate nanoparticles (NPs) for a given application. This requires the development of methodologies allowing, simultaneously, the unraveling of the NPs geometry and the screening of their reactivity. Herein, nanoimpact electrochemistry (NIE) allows for quantifying the transformation and measuring the electrocatalytic activity for the oxygen evolution reaction (OER) of >100 Ni(OH)2 NPs of a wide range of size (NP radii from 25 to 100 nm). This is achieved by scanning electrochemical microscopy in a generation/collection-like mode, with one electrode being used to electrogenerate by local precipitation colloidal Ni(OH)2 NPs and the second one being used to collect them by NIE. It allows (i) quantifying the reductive and oxidative conversion of the Ni(OH)2 NPs and (ii) separating the electrochemical conversion and the OER electrocatalysis, leading to the evaluation of a structure-activity relationship.
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Electrodeposition of earth-abundant iron group metals such as nickel is difficult to characterize by simple electrochemical analyses since the reduction of their metal salts often competes with inhibiting reactions. This makes the mechanistic interpretation sometimes contradictory, preventing unambiguous predictions about the nature and structure of the electrodeposited material. Herein, the complexity of Ni nanoparticles (NPs) electrodeposition on indium tin oxide (ITO) is unraveled operando and at a single entity NP level by optical microscopy correlated to ex situ SEM imaging. Our correlative approach allows differentiating the dynamics of formation of two different NP populations, metallic Ni and Ni(OH)2 with a <25â nm limit of detection, their formation being ruled by the competition between Ni2+ and water reduction. At the single NP level this results in a self-terminated growth, an information which is most often hidden in ensemble averaged measurements.
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While numerous efforts have been made toward the design of sustainable and efficient nanocatalysts of the hydrogen evolution reaction, there is a need for the operando observation and quantification of the formation of gas nanobubbles (NBs) involved in this electrochemical reaction. It is achieved herein through interference reflection microscopy coupled to electrochemistry and optical modeling. In addition to analyzing the geometry and growth rate of individual NBs at single nanocatalysts, the toolbox offered by superlocalization and quantitative label-free optical microscopy allows analyzing the geometry (contact angle and footprint with surface) of individual NBs and their growth rate. It turns out that, after a few seconds, NBs are steadily growing while they are fully covering the Pt nanoparticles that allowed their nucleation and their pinning on the electrode surface. It then raises relevant questions related to gas evolution catalysts, such as, for example, does the evaluation of NB growth at the single nanocatalyst really reflect its electrochemical activity?
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O2 activation under mild conditions remains a weighty challenge for chemists. Herein we report a study of electrochemical O2 reductive activation catalyzed by FeIII(F20TPP)Cl, by means of cyclic voltammetry and UV-vis spectroelectrochemistry in acidic solutions of N,N-dimethylformamide. Two parallel catalytic pathways have been evidenced occurring at different overpotentials. At high overpotential a classical electron-proton (EPT) pathway where protonation of Fe peroxo ultimately leads to the formation of high-valent Fe oxo species dominates. At low overpotential a proton-electron (PET) pathway involving a hydrosuperoxo species has been identified.
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Silver based ionic crystal nanoparticles (NPs) are interesting nanomaterials for energy storage and conversion, e.g. their colloidal solutions could be used as a reversible redox nanofluid in semi-solid redox flow cells. In this context, the reductive transformation of Brownian silver halide, AgX, NPs into silver NPs is probed by single NP electrochemistry, complemented by operando high resolution monitoring. However, their light sensitivity and poor conductivity make the operando monitoring of their chemical activity challenging. The electrochemical collisions of single AgX NPs onto a negatively biased electrode evidence a full conversion through multiple reduction steps within 3-10 ms. This is further corroborated by simulation of the conversion process and operando through a high resolution optical microscopy technique (Backside Absorbing Layer Microscopy, BALM). Both techniques are interesting strategies to infer at the single NP level the intrinsic charge capacity and charging rate of redox active Brownian nanomaterials, demonstrating the interest of the fast and reversible AgX/Ag system as a redox nanofluid.
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Herein we report the first example of using scanning electrochemical microscopy (SECM) to quantitatively analyze O2 reductive activation in organic media catalyzed by three different Fe porphyrins. For each porphyrin, SECM can provide in one single experiment the redox potential of various intermediates, the association constant of FeII with O2 , and the pKa of the FeIII (OOH- )/ FeIII (OO2- ) couple. The results obtained can contribute to a further understanding of the parameters controlling the catalytic efficiency of the Fe porphyrin towards O2 activation and reduction.
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By shortening solid-state diffusion times, the nanoscale size reduction of dielectric materials-such as ionic crystals-has fueled synthetic efforts toward their use as nanoparticles, NPs, in electrochemical storage and conversion cells. Meanwhile, there is a lack of strategies able to image the dynamics of such conversion, operando and at the single NP level. It is achieved here by optical microscopy for a model dielectric ionic nanocrystal, a silver halide NP. Rather than the classical core-shrinking mechanism often used to rationalize the complete electrochemical conversion and charge storage in NPs, an alternative mechanism is proposed here. Owing to its poor conductivity, the NP conversion proceeds to completion through the formation of multiple inclusions. The superlocalization of NP during such heterogeneous multiple-step conversion suggests the local release of ions, which propels the NP toward reacting sites enabling its full conversion.
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Nanopartículas del Metal/química , Nanopartículas/químicaRESUMEN
Most protocols developed to synthesize nanoparticles (NPs) and to control their shape are inspired from nucleation and growth theories. However, to rationalize the mechanisms of the shape-selective synthesis of NPs, experimental strategies allowing to probe in situ the growth of NPs are needed. Herein, metal Au or Ag nanoparticles (NPs) are produced by reaction of a metallic ion precursor with a reversible redox reducer. The process is explored by an oxidative electrosynthesis strategy using a sacrificial Au or Ag ultramicroelectrode to both trigger the metallic ion generation and control the local concentrations of the different reactants. The effect of the driving force for the metallic ion reduction over metal NP growth dynamics is inspected in situ and in real time at the single NP level by high-resolution optical microscopy from the tracking of the Brownian trajectories of the growing NPs in solution. The NP reductive growth/oxidative etching thermodynamics, and consequently the NP shape, are shown to be controlled electrochemically by the reversible redox couple, while the intervention of an Au(i) intermediate ion is suggested to account for the formation of gold nanocubes.
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The interest in nano-objects has recently dramatically increased in all fields of science, and electrochemistry is no exception. As a consequence, in situ and operando visualization of electrochemical processes is needed at the nanoscale. Herein, we propose a new interferometric microscopy based on an antireflective thin metal electrode layer. The technique is coupled to electrochemistry in a model example: the electro-deposition of Ag metallic nanoparticles (NPs). This challenges the current opto-electrochemical methods and even those relying on nano-impact detection. Indeed, the sensitivity allows the dynamic in situ visualization of the electrochemical growth and dissolution of individual Ag NPs, whose size was tracked dynamically down to 15 nm in diameter. The use of microelectrodes provides interesting quantitative analysis of the NPs, from optically resolved arrays of single NPs to condensed arrays of (unresolved) NPs. Particularly, the optical analysis of all the individual NPs allows the reconstruction of optical voltammograms similar to the electrochemical ones. Finally, the NP dissolution-redeposition is also investigated.
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Electrodeposition of nanoparticles (NPs) is a promising route for the preparation of highly electroactive nanostructured electrodes. By taking advantage of progressive electrodeposition, disordered arrays with a wide size distribution of Ag NPs are produced. Combined with surface-reaction monitoring by using highly sensitive backside absorbing-layer optical microscopy (BALM), such arrays offer a platform for screening size-dependent electrochemistry at the single NP level. In particular, this strategy allows rationalizing the electrodeposition dynamics at the single-NP level (>10â nm), up to the point of quantifying the presence of metal nanoclusters (<2â nm), and probing easier NP oxidation with size decrease, either through electrochemical or galvanic reactions.
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Some bacteria can act as catalysts to oxidize (or reduce) organic or inorganic matter with the potential of generating electrical current. Despite their high value for sustainable energy, organic compound production and bioremediation, a tool to probe the natural biodiversity and to select most efficient microbes is still lacking. Compartmentalized cell culture is an ideal strategy for achieving such a goal but the appropriate compartment allowing cell growth and electron exchange must be tailored. Here, we develop a conductive composite hydrogel made of a double network of alginate and carbon nanotubes. Homogeneous mixing of carbon nanotubes within the polyelectrolyte is obtained by a surfactant assisted dispersion followed by a desorption step for triggering electrical conductivity. Dripping the mixture in a gelling bath through simple extrusion or a double one allows the formation of either plain hydrogel beads or liquid core hydrogel capsules. The process is shown to be compatible with the bacterial culture (Geobacter sulfurreducens). Bacteria can indeed colonize the outer wall of plain beads or the inner wall of the conductive capsules' shell that function as an anode from which electrons produced by the cells are collected.