Scanning Electrochemical Microscopy Research Articles

EIS Investigation of a Single Pit on Cantor Alloy in Acidic Environment

High-entropy alloys (HEA) are an emerging class of materials with promising properties such as high strength and ductility, improved fatigue resistance, fracture toughness, and thermal stability. They show considerable potential for use as corrosion resistant alloys to support our infrastructure especially for use in extreme environments. In this work, we mainly focused on the typical Cantor alloy, which consists in a mixture of 5 elements CrMnFeCoNi in equimolar proportion. A huge amount of works has already been devoted to the study corrosion resistance of alloys in sulfuric acid [1] or in chloride containing solutions [2,3]. For the latter, the study of the pitting propagation remains challenging since this kind of corrosion initiates as a stochastic process.Electrochemical impedance spectroscopy (EIS) is intensively used as a tool for corrosion research and is well suited for the identification of complex mechanisms. However, data analysis remains difficult in the case of pitting studies, which can be described schematically as n anodic sites in parallel at different states of evolution. In this work we report on EIS analysis performed on a single pit (Fig. 1a) in order to describe the various step of its evolution as a function of time, but also as a function of various parameters such as the chloride ion concentration or the corrosion potential. Single pits were obtained by studying the breakdown of the passive film using the pumped-micropipette delivery/substrate collection (Pumped-MD/SC) mode of scanning electrochemical microscopy (SECM). A detailed mechanism is proposed to account for EIS results obtained on a single pit (Fig. 1b) in order to explain results on usuals EIS measurements.[1] J. Yang, J. Wu, C. Y. Zhang, S. D. Zhang, B. J. Yang, W. Emori et J. Q. Wang, « Effects of Mn on the electrochemical corrosion and passivation behavior of CoFeNiMnCr high-entropy alloy system in H2SO4 solution », Journal of Alloys and Compounds, 819, avril 2020, p. 152943, https://doi.org/10.1016/j.jallcom.2019.152943[2] Camila Boldrini Nascimento, Uyime Donatus, Carlos Triveño Ríos et Renato Altobelli Antunes, « Electronic properties of the passive films formed on CoCrFeNi and CoCrFeNiAl high entropy alloys in sodium chloride solution », Journal of Materials Research and Technology, 9, no 6, novembre 2020, p. 13879-92, https://doi.org/10.1016/j.jmrt.2020.10.002[3] Mengjiao Li, Qingjun Chen, Xia Cui, Xinyuan Peng et Guosheng Huang, « Evaluation of corrosion resistance of the single-phase light refractory high entropy alloy TiCrVNb0.5Al0.5 in chloride environment », Journal of Alloys and Compounds, 857, mars 2021, p. 158278, https://doi.org/10.1016/j.jallcom.2020.158278 Figure 1

Measuring Double Layer Charging Via Droplet Approach Technique

The potential of zero-charge (PZC) is an important property of the electrochemical double layer (EDL) that has been shown to correlate with changes in the activities of several important reactions such as the oxygen reduction reaction (ORR) and the hydrogen evolution reaction (HER)1. This property was historically measured on droplet mercury electrodes (DME) where surface tension was measured vs potential, an experiment difficult to perform with other metal electrodes. Electrochemical impedance spectroscopy, cyclic voltammetry and galvanic discharge have been widely used to elucidate double layer capacitance but make several assumptions about the ideality of the double layer, measurement system, physical model employed, and have suffered from irreproducibility. The potential of maximum entropy (PME), where the solvent molecules are most disordered, has been measured via the laser induced temperature jump (LITJ) technique which works well when there is no specific adsorption2. A multiple approach mode of scanning electrochemical cell microscopy (SECCM) has also been used to measure local PZCs of polycrystalline3 and high-entropy alloy electrodes4. The SECCM approach is similar to an older immersion method that is not often used5. In this work we create a simple droplet type cell with a pneumatic sample stage to enable a simplified and less expensive version of the SECCM approach/immersion experiments and compare the results to those obtained via the LITJ method.

Accelerating the Discovery of Oxygen Reduction Electrocatalysts: High‐Throughput Screening of Element Combinations in Pt‐Based High‐Entropy Alloys

AbstractThe vast number of element combinations and the explosive growth of composition space pose significant challenges to the development of high‐entropy alloys (HEAs). Here, we propose a procedural research method aimed at accelerating the discovery of efficient electrocatalysts for oxygen reduction reaction (ORR) based on Pt‐based quinary HEAs. The method begins with an element library provided by a large language model (LLM), combined with microscale precursor printing and pulse high‐temperature synthesis techniques to prepare multi‐element combination HEA array in one step. Through high‐throughput measurement using scanning electrochemical cell microscopy (SECCM), precise identification of highly active HEA element combinations and exploration of composition space for a specific combination are achieved. Advantageous element combinations are further validated in practical electrocatalytic evaluations. The contributions of individual element sites and the synergistic effects among elements of such HEAs in enhancing reaction activity are elucidated via density functional theory (DFT) calculations. This method integrates high‐throughput experiments, practical catalyst validation, and DFT calculations, providing a new pathway for accelerating the discovery of efficient multi‐element materials in the field of energy catalysis.

Defect Engineering of WO3 by Rapid Flame Reduction for Efficient Photoelectrochemical Conversion of Methane into Liquid Oxygenates

Photoelectrochemical (PEC) conversion is a promising way to utilize methane (CH4) as a chemical building block without harsh conditions. However, PEC CH4 conversion to value-added chemicals remains challenging due to the thermodynamically favorable over-oxidation of CH4. Here, we report WO3 nanotubes (NTs) photoelectrocatalysts for PEC CH4 conversion with high liquid product selectivity through defect engineering. By tuning the flame reduction treatment, the oxygen vacancies of WO3 NTs were carefully controlled. The optimally reduced WO3 NTs suppressed over-oxidation of CH4 showing high total C1 liquid selectivity of 69.4% and production rate of 0.174 μmol⋅cm-2⋅h-1. Scanning electrochemical microscopy revealed that oxygen vacancies can restrain the production of hydroxyl radicals, which in excess could further oxidize C1 intermediates to CO2. Additionally, band diagram analysis and computational studies elucidated that oxygen vacancies thermodynamically suppress over-oxidation. This work introduces a strategy to understand and control the selectivity of photoelectrocatalysts for direct CH4 conversion to liquids.

Development of an in situ Mediator Dosing Concept for Scanning Electrochemical Microscopy in Lithium‐Ion Battery Research

AbstractIn scanning electrochemical microscopy (SECM), the addition of a redox active species plays an essential role. Those deliberately added mediators may alter results in SECM studies. In investigations of lithium‐ion battery (LIB) materials, especially of the positive electrode, the oxidation potentials of commonly used mediator substances such as ferrocene are located within the operation potential of the electrode. Thus, they possibly interfere with the regular charge/discharge processes. In situ studies are therefore in need of approaches reducing or eliminating the use of mediators. Within this publication, a novel mediator dosing (MD) concept is introduced. A capillary was closely positioned at the tip of the scanning probe. By gravity flow, stable flow rates of mediator solution of up to 32.4±0.6 μL h−1 were achieved. These low amounts were found to be sufficient to form a ferrocene zone at the probe tip enabling feedback mode SECM measurements with comparable quality to measurements directly in ferrocene solution. Proof of concept experiments were conducted by investigation of a thin‐film electrode with a micro‐structured surface. Furthermore, the MD concept was applied in imaging experiments of a commercially available LIB graphite electrode.

In-situ electrochemical mapping of local activity on Zn and Zn-Al alloy electrodes by scanning electrochemical microscopy

Alternating-current scanning electrochemical microscopy (AC-SECM) is introduced to monitor the local activity of Zn and Zn-10Al alloy electrodes. In-situ AC-SECM maps at potentials near the open circuit potential (OCP) in 2 M NaCl (pH 10) indicate that the surfaces of Zn and Zn-10Al alloy electrodes are covered with the passivation layer. When the electrolyte is exchanged with a 0.1 M ethylenediaminetetraacetic acid (EDTA) containing electrolyte, AC-SECM maps at the potential near the OCP clearly reveal the active Zn and the distinct difference between Al- and Zn-rich phases. Thereby, it is demonstrated that EDTA enhances the electrochemical activities of Zn and Zn-10Al alloy electrodes. With shifting the potential to anodic potential of −1.0 V in 0.1 M EDTA containing electrolyte, the interfacial difference between Al- and Zn-rich phases slowly disappears in AC-SECM maps, confirming that the local activity of the surface observed by AC-SECM is only attributed to the metal-EDTA complex. It is noteworthy that the hindered diffusion at the confined space between the tip and the substrate (∼ 10 µm) certainly influences on the local activities of Zn and Zn-10Al alloy electrodes. Additionally, AFM results indicate that the slightly different interactions of EDTA with Al- and Zn-rich phases cause the roughness contrast.

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.

Investigating mass transport in Li-ion battery electrodes using SECM and SICM

Lithium-ion batteries (LIBs) are indispensable as global energy production transitions to sustainable production. Nevertheless, the use of LIBs in renewable energy storage applications is challenging due to their limited power densities. To comprehend the origin of this limitation, it is crucial to investigate the effect of electrode architecture on the Li+ ion transport within their pores (solution-phase). In this work, the solution phase transport in various porous Li4Ti5O12 (LTO) films was investigated using scanning ion conductance microscopy (SICM) and scanning electrochemical microscopy (SECM). When the porosity of LTO film increases, SECM and SICM approach curves show an increase in current. This is attributed to the ion transport through the film pores. The 2D topographical mapping using both techniques shows their ability to detect the LTO film's heterogeneity. Most importantly, this work gives insight into the complementary nature of the two scanning probe techniques as demonstrated by the comparable MacMullin numbers.

Atomically Dispersed Ru-doped Ti4O7 Electrocatalysts for Chlorine Evolution Reaction with a Universal Activity.

Chlorine has been supplied by the chlor-alkali process that deploys dimensionally stable anodes (DSAs) for the electrochemical chlorine evolution reaction (ClER). The paramount bottlenecks have been ascribed to an intensive usage of precious elements and inevitable competition with the oxygen evolution reaction. Herein, a unique case of Ru2+-O4 active motifs anchored on Magnéli Ti4O7 (Ru-Ti4O7) via a straightforward wet impregnation and mild annealing is reported. The Ru-Ti4O7 performs radically active ClER with minimal deployment of Ru (0.13 wt%), both in 5 m NaCl (pH 2.3) and 0.1 m NaCl (pH 6.5) electrolytes. Scanning electrochemical microscopy demonstrates superior ClER selectivity on Ru-Ti4O7 compared to the DSA. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a universally active ClER (over a wide range of pH and [Cl-]), through a direct adsorption of Cl- on Ru2+-O4 sites as the most plausible pathway, together with stabilized ClO* at low [Cl-] and high pH.

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.

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.

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.

Impedimetric Measurement of Exchange Currents and Ionic Diffusion Coefficients in Individual Pseudocapacitive Nanoparticles.

Among electroanalytical techniques, electrochemical impedance spectroscopy (EIS) offers the unique advantage of a high degree of frequency resolution. This enables EIS to readily deconvolute between the capacitive, resistive, and diffusional processes that underlie electrochemical devices. Here, we report the measurement of impedance spectra of individual, pseudocapacitive nanoparticles. We chose Prussian blue as our model system, as it couples an electron-transfer reaction with sodium ion intercalation-processes which, while intrinsically convoluted, can be readily resolved using EIS. We used a scanning electrochemical cell microscope (SECCM) to isolate single Prussian blue particles in a microdroplet and measured their impedance spectra using the multi-sine, fast Fourier transform technique. In doing so, we were able to extract the exchange current density and sodium ion diffusivity for each particle, which respectively inform on their electronic and ionic conductivities. Surprisingly, these parameters vary by over an order of magnitude between particles and are not correlated to particle size nor to each other. The implication of this apparent heterogeneity is that in a hypothetical battery cathode, one active particle may transfer electrons 10 times faster than its neighbor; another may suffer from sluggish sodium ion transport and have restricted charging rate capabilities compared to a better-performing particle elsewhere in the same electrode. Our results inform on this intrinsic heterogeneity while demonstrating the utility of EIS in future single-particle studies.

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.