Scanning Electrochemical Microscopy Research Articles

Ag-La(OH)3@Dy2O3 hybrid composite modified laser-induced graphene surface for simultaneous electrochemical detection of bisphenol A and tartrazine

Laser-induced graphene (LIG), created through CO2 laser irradiation of polyimide film (PI) substrates, has emerged as a versatile and promising material in numerous fields. However, despite its potential, a comprehensive exploration of LIG’s surface structure and reactivity remains absent in the literature, which is crucial for advancing its applications in electrochemical and electroanalytical fields. In this study, we developed and examined the interfacial structure and electronic behavior of an Ag-La(OH)3@Dy2O3 hybrid composite-modified LIG system as a model. We employed scanning electrochemical microscopy (SECM) to investigate these properties, extending our analysis to the simultaneous detection of organic pollutants, such as bisphenol A (BPA) and tartrazine (TRZ), in real samples. Compared to previous LIG production techniques, the LIG-modified electrode demonstrated a high electron transfer rate at the interface. The tailored LIG substrate showed excellent electrochemical activity towards electrochemical oxidation and simultaneous electroanalytical applications for BPA and TRZ with low detection limits (BPA: 9.2 nM, TRZ: 0.96 nM) in neutral physiological conditions. As a proof of concept, an extension to the real-time application of simultaneous monitoring of BPA and TRZ in various food samples was successfully demonstrated.

Understanding the Unique Corrosion Phenomenon of Sanxingdui Embrittled Gold Masks Using Scanning Electrochemical Cell Microscopy (SECCM): Intergranular Corrosion of Au-Ag-Pb Ternary Alloy

The study investigated the rare corrosion of embrittled gold masks excavated from the Sanxingdui archaeological site, attributing the embrittlement to preferential corrosion of intergranular Pb-containing phases through morphological studies using metallographic microscopy and SEM-EDS. Scanning electrochemical cell microscopy (SECCM) technology was used to quantitatively analyze simulated Au-Ag-Pb alloy samples to compare the electrochemical properties of different phases at the microscopic level. The results revealed an electrochemical activity order of Au-Ag < Au2Pb < AuPb2+PbxOy, which explains the varying levels of retention for different components in gold masks and provides a reference for subsequent conservation strategy.

Triple-function carbon-based Ca2+ ion-selective pH ring microelectrode to study real-time bacteria-mediated hydroxyapatite corrosion

BackgroundThe local pH change mediated by the pathogenic bacterial species Streptococcus mutans plays a significant role in the corrosion of hydroxyapatite (HA) present in the tooth in the dynamic oral cavity. The acid produced by the bacteria decreases the local pH and releases Ca2+ ions from the HA. We studied the bacteria-mediated demineralization of HA by scanning electrochemical microscopy (SECM) after growing S. mutans biofilm on HA for 7 days. ResultsWe notably developed a triple-function SECM-compatible tip that could be positioned above the biofilm. It can also measure the pH and [Ca2+] change simultaneously above the biofilm-HA substrate. The triple-function SECM tip is a combination of a potentiometric pH sensor deposited with iridium oxide and a dual-function carbon-based Ca2+ ion-selective membrane electrode with a slope of 67 mV/pH and 34.3 mV/log [Ca2+], respectively. The distance-controlled triple-function SECM tip monitored real-time pH and [Ca2+] changes 30 μm above the S. mutans biofilm. The high temporal resolution pH data demonstrated that after approximately 20 min of sucrose addition, S. mutans started to produce acid to titrate the solution buffer, causing a pH change from 7.2 to 6.5 for HA and from 7.2 to 5 for the glass substrate. We observed that, after 30 min of acid production, ∼300 μM of Ca2+ ions were increased at pH 6.5 above the biofilm surface as a result of the pH change in the local microenvironment. After the release of Ca2+ from HA, the pH environment again shifted toward the neutral side, from 6.5 to 7.2. Therefore, precipitation of Ca2+ happens at the top of the biofilm, thus corroding the HA from underneath. For a glass substrate, in contrast, no Ca2+ ions were released, and the pH did not change back to 7.2. We were able to observe the dynamics of the HA demineralization–remineralization process simultaneously with our newly developed triple-function SECM tip or microprobe. SignificanceThis technique could notably advance the study of similar complex processes, such as bacteria-mediated corrosion in biomedical and environmental contexts.

Modeling Scanning Electrochemical Cell Microscopy (SECCM) in Twisted Bilayer Graphene.

Twisted 2D-flat band materials host exotic quantum phenomena and novel moiré patterns, showing immense promise for advanced spintronic and quantum applications. Here, we evaluate the nanostructure-activity relationship in twisted bilayer graphene by modeling it under the scanning electrochemical cell microscopy setup to resolve its spatial moiré domains. We solve the steady state ion transport inside a 3D nanopipette to isolate the current response at AA and AB domains. Interfacial reaction rates are obtained from a modified Marcus-Hush-Chidsey theory combining input from a tight binding model that describes the electronic structure of bilayer graphene. High rates of redox exchange are observed at the AA domains, an effect that reduces with diminished flat bands or a larger cross-sectional area of the nanopipette. Using voltammograms, we identify an optimal voltage that maximizes the current difference between the domains. Our study lays down the framework to electrochemically capture prominent features of the band structure that arise from spatial domains and deformations in 2D flat-band materials.

Superatomic Layer of Cubic Mo4S4 Clusters Connected by Cl Cross-Linking.

Superatomic clusters - assemblies of atoms with various sizes, shapes, and compositions - can form hierarchical architectures that exhibit emergent electronic properties not found in their individual units. In particular, cubic M4X4 clusters of chalcogenides (M = transition metal; X = chalcogen) are recognized as versatile building blocks for 3D structures with tunable morphologies and electronic properties. However, tetrahedral M4X4 clusters rarely assemble into 2D architectures, which could offer a distinct class of functional materials from their 3D analogues. Here, this work reports the preparation of 2D Mo8S8Cl11, a superatomic layer with a sandwich structure consisting of Mo4S4 clusters interconnected through Cl cross-linking. The vapor-phase reaction inside nanotubes promotes the selective growth of Mo8S8Cl11 nanoribbons, allowing detailed characterization via transmission electron microscopy. This methodology can be applied to the growth of layered structures containing Mo8S8Cl11 at the micrometer scale. This work has demonstrated that mono- and few-layer Mo8S8Cl11 can be prepared by exfoliation of parent solids. Electronic structure calculations indicate that the 2D monolayer has quasi-flat bands, giving rise to an indirect-to-direct bandgap transition under mechanical strain. Furthermore, scanning electrochemical microscopy reveals the potential of the layered structures as highly efficient catalysts for the hydrogen-evolution reaction.

Highthroughput Screening of CuBi Bimetallic Catalyst Array for Electrocatalytic CO2Reduction Reaction by Scanning Electrochemical Microscope.

The testing and evaluation of catalysts in CO2electroreduction is a very tedious process. To study the catalytic system of CO2reduction more quickly and efficiently, it is necessary to establish a method that can detect multiple catalysts at the same time. Herein, a series of CuBi bimetallic catalysts have been successfully prepared on a single glass carbon electrode by a scanning micropieptte contact method. The application of scanning electrochemical microscopy (SECM) enabled the visualization of the CO2reduction activity in diverse catalyst micro-points. The SECM imaging with Substrate generation/tip collection (SG/TC) mode was conducted on CuBi bimetallic micro-points, revealing that HER reaction emerged as the prevailing reaction when a low overpotential was employed. While the applied potential was lower than -1.5 V (vs Ag/AgCl), the reduction of CO2to formic acid became dominant. Increasing the bismuth proportion in the bimetallic catalyst can inhibit the hydrogen evolution reaction at low potential and enhances the selectivity of the CO product at high cathode overpotential.This research offers a novel approach to examining arrays of catalysts for CO2reduction.

Particle Size-Tunable Polydopamine Nanoparticles for Optical and Electrochemical Imaging of Latent Fingerprints on Various Surfaces.

Powder dusting method is the most widely used approach due to its low cost, simplicity, minimal instrument dependence, and extensive applicability for developing latent fingerprints (LFPs). Herein, a novel optical and electrochemical dual-mode method for high-resolution LFP enhancement has been explored based on size-tunable polydopamine (PDA) nanoparticles (NPs) and scanning electrochemical microscopy (SECM). Dark PDAs rich in functional groups and negative charges can combine with the residues of LFPs on various surfaces with high sensitivity and selectivity to realize high-resolution visual fingerprint physical patterns on various porous and nonporous substrates with light color. However, optical visualization is not feasible for LFPs on dark or multicolored surfaces. Fortunately, based on the differences in electrochemical reactivity between ridges and furrows caused by the conductivity and reducibility of PDA powders, SECM can serve as a powerful supplement to optical methods to effectively overcome background color interference and distinctly display fingerprint patterns. Intriguingly, it is noteworthy that the binding amount and particle size of PDA powder significantly affected the optical and electrochemical visualization of LFPs: more powder binding amounts provided darker ridges in optical, and more surface reaction sites (larger powder binding mass at the same particle size or smaller particle size at the same mass) provided higher currents of ridges in electrochemical imaging. It demonstrates that the PDA powder as a dual-mode developer for LFPs offers a promising method for individual identification in forensics.

General Method for Fitting Kinetics from the SECM Images of Reactive Sites on Flat Surfaces.

Scanning electrochemical microscopy (SECM) is a technique for imaging electrochemical reactions at a surface. The interaction between electrochemical reactions occurring at the sample and scanning electrode tip is quite complicated and requires computer modeling to obtain quantitative information from SECM images. Often, existing computer models must be modified, or a new model must be created from scratch to fit kinetic parameters for different reactive features. This work presents a method that can simulate the SECM image of a reactive feature of any shape on a flat surface which is coupled to a computer program which effectuates the automated fitting of kinetic information from these images. This fitting program is evaluated along with several methods for estimating the shapes of reactive features from their SECM images. Estimates of the reactive feature shape from SECM images were not sufficiently accurate and produced median relative errors for the surface rate constant that were >50%. Fortunately, more precise techniques for imaging the reactive features such as optical microscopy can supply sufficiently accurate shapes for the fitting procedure to produce accurate results. Fits of simulated SECM images using the actual shape from the simulation produced median relative errors for the surface rate constant that were <10% for the smallest reactive features tested. This method was applied to the SECM images of aluminum alloy AA7075 which revealed diffusion-limited kinetics for ferrocene methanol reduction over inclusions in the surface of the alloy.

Comprehensive electrochemical imaging analyses of redox activities correlated to multilayer graphene and graphite structures

The utilization of two-dimensional (2D) materials within electrochemical devices constitutes a pivotal area of investigation, particularly pertinent to energy-related materials. Scanning electrochemical cell microscopy (SECCM) stands as a valuable characterization tool for the in-situ visualization of electrochemical processes transpiring within nanoscale structures. In the context of this investigation, SECCM was employed to scrutinize the influence of atomic structures in multilayer graphene and graphite samples, emblematic of 2D materials, upon a spectrum of electrochemical reactions, encompassing redox reactions of Ru(NH3)63+/2+. By visualizing and locally evaluating electrochemical reactions with various atomic structures, this research can be applied to design materials to promote more electrochemical reactions, as well as to other electrochemical energy devices (such as lithium-ion batteries and electrocatalysts). Furthermore, it extends its purview to assess the applicability of graphene substrates as platforms for the evaluation of other two-dimensional materials.

Correlating Thickness and Phase of Single Co(OH)2 Micro-Platelets to the Intrinsic Activity of Oxygen Evolution Electrocatalysis.

Morphology, crystal phase, and its transformation are important structures that frequently determine electrocatalytic activity, but the correlations of intrinsic activity with them are not completely understood. Herein, using Co(OH)2 micro-platelets with well-defined structures (phase, thickness, area, and volume) as model electrocatalysts of oxygen evolution reaction, multiple in situ microscopy is combined to correlate the electrocatalytic activity with morphology, phase, and its transformation. Single-entity morphology and electrochemistry characterized by atomic force microscopy and scanning electrochemical cell microscopy reveal a thickness-dependent turnover frequency (TOF) of α-Co(OH)2. The TOF (≈9.5 s-1) of α-Co(OH)2 with ≈14nm thickness is ≈95-fold higher than that (≈0.1 s-1) with ≈80nm. Moreover, this thickness-dependent activity has a critical thickness of ≈30nm, above which no thickness-dependence is observed. Contrarily, β-Co(OH)2 reveals a lower TOF (≈0.1 s-1) having no significant correlation with thickness. Combining single-entity electrochemistry with in situ Raman microspectroscopy, this thickness-dependent activity is explained by more reversible Co3+/Co2+ kinetics and larger ratio of active Co sites of thinner α-Co(OH)2, accompanied with faster phase transformation and more extensive surface restructuration. The findings highlight the interactions among thickness, ratio of active sites, kinetics of active sites, and phase transformation, and offer new insights into structure-activity relationships at single-entity level.

Electrochemical CO2 Reduction at Surface Modified Silver Nanoparticles

CO2 capture and transformation into chemical fuels presents a useful carbon-neutral energy source to curb the effects of global warming if the electrocatalyst used is highly active, exhibits sufficient product selectivity, and is energetically efficient. Metal nanoparticles (NPs) have emerged as a promising class of catalysts for the electrochemical CO2 reduction reaction (CO2RR) and their product selectivity are expected to be further improved through surface modification with different ligands. The primary objective of this work is to compare the use of Scanning Electrochemical Microscopy (SECM) and Rotating Ring Disk Electrode (RRDE) to study CO2 reduction at silver nanoparticles (Ag NPs) modified with amino acids (cysteine and tryptophan) and Ag NPs synthesized by a citrate reduction method. RRDE studies showed the onset potential for CO2RR was earlier for both the Ag NPs with cysteine and Ag NPs with tryptophan than those with citrate. SECM showed earlier onset potentials for CO2RR than the RRDE experiment for every type of Ag NP as well as higher sensitivity in detecting the major CO2RR products such as formate and CO. SECM also showed less hydrogen formation for the Ag NPs with cysteine and Ag NPs with tryptophan.

Evaluating the impact of iron impurities in KOH on OER performance of BaNiO3 single crystals using scanning electrochemical cell microscopy

Understanding the oxygen evolution reaction (OER) electrocatalysis requires a careful understanding of the surface and activity evolution of well-defined materials. An especially promising candidate is the BaNiO3 hexagonal perovskite, matching strides with benchmark catalysts such as Ba0.5Sr0.5Co0.8Fe0.2O3–δ. Here, we conducted a structural and electrochemical analysis of BaNiO3 single crystals to assess the influence of iron impurities in KOH electrolyte on their OER performance. We used scanning electrochemical cell microscopy (SECCM) for precise measurements on BaNiO3 single crystals in the absence of carbon additives. Cyclic voltammetry (CV) revealed that the presence of iron consistently enhanced the OER current with subsequent cycles, indicating a dynamic improvement in BaNiO3's electrochemical activity. Conversely, in iron-free KOH electrolyte, performance diminished with cycling. These findings not only underscore the critical necessity of KOH purification for BaNiO3 electrochemical studies but also showcase SECCM's unparalleled ability to offer insights into the electrochemical evolution of individual entities such as single crystals. This makes it a powerful operando tool for evaluating forthcoming single crystals, thereby aiding in the design of superior catalysts for OER reactions.

Pit initiation in quenching and partitioning processed martensitic stainless steels

The present article investigates the influence of chemical composition and phase fractions on the corrosion behaviour of industrially produced quenching and partitioning (Q&P) martensitic stainless steels. Localised corrosion was analysed by scanning Kelvin probe force microscopy (SKPFM) and scanning electrochemical microscopy (SECM) in 3.5 wt.% NaCl solution. SKPFM revealed a Volta-potential difference of around 40 mV between inclusions and the matrix, which is larger than the Volta potential variations within the matrix. This difference in surface potential is a driving force for selective dissolution (corrosion initiation) at inclusions and inclusion/matrix interfaces. SECM detected early pitting initiation, particularly in alloys containing MnS and TiN inclusions. Results suggest that pitting initiation and propagation occur at those specific regions. This study emphasised that irrespective of chemical composition and phase fraction, localised corrosion initiation in Q&P-processed martensitic stainless steels is predominantly governed by the presence of inclusions.

Fabrication and characterization of hydroxyapatite coatings on anodized magnesium alloys by electrochemical and chemical methods intended for biodegradable implants

The fabrication of hydroxyapatite (HAP)/MgO composite coatings on Mg alloy is crucial for enhancing the corrosion resistance and biocompatibility of biomedical implants. In this study, we aimed to investigate the effects of two different surface modification methods, i.e., electrochemical (electrodeposition, ED) and chemical (solution treatment, ST), on the phase structure, degradation properties, and biocompatibility of the composite coatings in comparison to the anodized coating. The surface morphologies and crystalline structures of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Subsequently, the degradation rate of the coatings in simulated body fluid were comprehensively evaluated by using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and scanning electrochemical microscopy (SECM) tests. Additionally, in-vitro cell proliferation assays were employed to quantitatively assess the biocompatibilities of the coatings. The results showed that both ED and ST methods were effective in depositing HAP on anodized Mg alloy, resulting in different surface morphologies with hydroxyapatite layer thicknesses of 2.71 μm and 3.56 μm, respectively. In this way, the HAP-deposited coatings exhibited improved corrosion resistances and biocompatibilities compared with those of the anodized coating. Specifically, the ST-deposited composite film displayed superior degradability and biocompatibility which was attributed to its filiform surface morphology and thicker HAP layer. Overall, the present study demonstrates the potential of HAP/MgO composite coatings for biomedical applications, with implications for the development of advanced implant materials with improved performance and biocompatibility.

Integration of Scanning Electrochemical Microscopy and Scanning Electrochemical Cell Microscopy in a Bifunctional Nanopipette toward Simultaneous Mapping of Activity and Selectivity in Electrocatalysis.

Scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) were integrated in a single bifunctional probe for simultaneous mapping of the oxygen reduction current and the oxidation current of the produced H2O2. The dual probe is fabricated from a double-barrel θ capillary, comprising one open barrel filled with the electrolyte and another filled with pyrolytic carbon. Pt is deposited with a gas injection system (GIS) at the end of the carbon barrel. The probe integrates the advantages of both SECM and SECCM by forming an electrochemical droplet cell that embeds the Pt working electrode of the carbon barrel directly into the electrolyte meniscus formed upon sample contact from the electrolyte barrel. The versatility of the dual probe is demonstrated by mapping the oxygen reduction reaction (ORR) current and the H2O2 oxidation current of a Pt microstrip on a gold substrate. This allows simultaneous localized electrochemical measurements, highlighting the potential of the dual probe for broader applications in characterizing the electrocatalytic properties of materials.

Anodic H2O2 generation in carbonate‐based electrolytes – Mechanistic insight from scanning electrochemical microscopy

For the anodic H2O2 generation, it has been shown that the electrolyte composition can steer the reaction pathway toward increased H2O2 generation. Previous efforts made on composition optimization found that the impact of the molar fraction of carbonate species varies for different anodes, and therefore, controversies remain concerning the reaction pathways as well as the species involved in H2O2 formation. Considering that water oxidation results in the liberation of protons within the anode microenvironment, the corresponding acidification would cause an equilibrium shift between carbonate species, which in turn may modulate the reaction pathway. We determined the changes in the fraction of carbonate species in the vicinity of an anode by performing local pH measurements using a Au nanoelectrode positioned in close proximity to an operating anode by shear‐force scanning electrochemical microscopy (SECM). It could be confirmed that the main anionic species at the interface is HCO3‐, at potentials where H2O2 is preferentially formed, regardless of the pH value in the bulk. The simultaneous use of a Au‐Pt double barrel microelectrode in generator‐collector SECM measurements demon­strates that the local HCO3‐ concentration is collectively determined by the oxidation current, buffer capacity, and bulk pH of the electrolyte.

Anodic H2O2 generation in carbonate‐based electrolytes – Mechanistic insight from scanning electrochemical microscopy

For the anodic H2O2 generation, it has been shown that the electrolyte composition can steer the reaction pathway toward increased H2O2 generation. Previous efforts made on composition optimization found that the impact of the molar fraction of carbonate species varies for different anodes, and therefore, controversies remain concerning the reaction pathways as well as the species involved in H2O2 formation. Considering that water oxidation results in the liberation of protons within the anode microenvironment, the corresponding acidification would cause an equilibrium shift between carbonate species, which in turn may modulate the reaction pathway. We determined the changes in the fraction of carbonate species in the vicinity of an anode by performing local pH measurements using a Au nanoelectrode positioned in close proximity to an operating anode by shear‐force scanning electrochemical microscopy (SECM). It could be confirmed that the main anionic species at the interface is HCO3‐, at potentials where H2O2 is preferentially formed, regardless of the pH value in the bulk. The simultaneous use of a Au‐Pt double barrel microelectrode in generator‐collector SECM measurements demon­strates that the local HCO3‐ concentration is collectively determined by the oxidation current, buffer capacity, and bulk pH of the electrolyte.

Label-Free Assessment of Neuron-Specific Enolase via Polydopamine over a Carbon-Nanotube-Based Flexible Immunosensor.

A label-free electrochemical immunosensor was developed for the rapid and sensitive detection of neuron-specific enolase (NSE). The electropolymerization of dopamine in conjunction with highly conductive carbon nanotubes offers a simple and quick platform for the direct anchoring of antibodies without the assistance of any coupling agent as well as a blocking agent. The developed immunosensor exhibited a wider detection range from 120 pM (9 ng mL-1) to 3 nM (200 ng mL-1) for NSE with a high sensitivity of 3.9 μA pM-1 cm-2 in 0.1 M phosphate-buffered saline (PBS) at physiological pH (7.4). Moreover, the short recognition time (15 min) for the antigen enabled the detection to be fast and less invasive. Additionally, the evaluation of a rate constant at various concentrations of NSE via feedback mode of scanning electrochemical microscopy (SECM) explained the profound effect of antigen concentration on the rate of flow of electrons. Therefore, the proposed immunosensor can be a promising tool for the early detection of small cell lung cancer in a very short period of time with consistent accuracy.

Nanoscale Quantitative Imaging of Single Nuclear Pore Complexes by Scanning Electrochemical Microscopy.

The nuclear pore complex (NPC) is a proteinaceous nanopore that solely and selectively regulates the molecular transport between the cytoplasm and nucleus of a eukaryotic cell. The ∼50 nm-diameter pore of the NPC perforates the double-membrane nuclear envelope to mediate both passive and facilitated molecular transport, thereby playing paramount biological and biomedical roles. Herein, we visualize single NPCs by scanning electrochemical microscopy (SECM). The high spatial resolution is accomplished by employing ∼25 nm-diameter ion-selective nanopipets to monitor the passive transport of tetrabutylammonium at individual NPCs. SECM images are quantitatively analyzed by employing the finite element method to confirm that this work represents the highest-resolution nanoscale SECM imaging of biological samples. Significantly, we apply the powerful imaging technique to address the long-debated origin of the central plug of the NPC. Nanoscale SECM imaging demonstrates that unplugged NPCs are more permeable to the small probe ion than are plugged NPCs. This result supports the hypothesis that the central plug is not an intrinsic transporter, but is an impermeable macromolecule, e.g., a ribonucleoprotein, trapped in the nanopore. Moreover, this result also supports the transport mechanism where the NPC is divided into the central pathway for RNA export and the peripheral pathway for protein import to efficiently mediate the bidirectional traffic.

Probing non-Faradaic process during elastic deformation in a single sphere of extremely soft mesoporous carbon

Mesoporous carbon materials, known as graphene mesosponges (GMS), exhibit remarkable flexibility. These materials are expected to advance the field of physical chemistry through the investigation of phenomena induced by significant deformation of mesopores when mechanical forces are applied. In this work, GMS has been synthesized in the form of spherical microparticles, namely micro-spherical GMS (ms-GMS). The remarkable flexibility of ms-GMS has been validated through mercury intrusion tests, and also by methanol adsorption measurements with and without the application of mechanical force. Moreover, we successfully capture live footage of the elastic deformation of a single ms-GMS particle, enabling the determination of ‘the Poisson's ratio. Furthermore, we are attempting to observe the non-Faradaic process that occurs within a single sphere during mechanical deformation, utilizing scanning electrochemical cell microscopy (SECCM). The results showed a noticeable decline in capacitive rate performance when the pore size decreased from 7 to 2 nm. This approach effectively minimizes interference from other structural variations that typically arise during carbon synthesis and electrode fabrication, offering a new avenue for elucidating the specific influence of pore size in such materials.