Active Electrode Surface Research Articles

Enhanced Electrochemiluminescence of Luminol and-Dissolved Oxygen by Nanochannel-Confined Au Nanomaterials for Sensitive Immunoassay of Carcinoembryonic Antigen.

Simple development of an electrochemiluminescence (ECL) immunosensor for convenient detection of tumor biomarker is of great significance for early cancer diagnosis, treatment evaluation, and improving patient survival rates and quality of life. In this work, an immunosensor is demonstrated based on an enhanced ECL signal boosted by nanochannel-confined Au nanomaterial, which enables sensitive detection of the tumor biomarker-carcinoembryonic antigen (CEA). Vertically-ordered mesoporous silica film (VMSF) with a nanochannel array and amine groups was rapidly grown on a simple and low-cost indium tin oxide (ITO) electrode using the electrochemically assisted self-assembly (EASA) method. Au nanomaterials were confined in situ on the VMSF through electrodeposition, which catalyzed both the conversion of dissolved oxygen (O2) to reactive oxygen species (ROS) and the oxidation of a luminol emitter and improved the electrode active surface. The ECL signal was enhanced fivefold after Au nanomaterial deposition. The recognitive interface was fabricated by covalent immobilization of the CEA antibody on the outer surface of the VMSF, followed with the blocking of non-specific binding sites. In the presence of CEA, the formed immunocomplex reduced the diffusion of the luminol emitter, resulting in the reduction of the ECL signal. Based on this mechanism, the constructed immunosensor was able to provide sensitive detection of CEA ranging from 1 pg·mL-1 to 100 ng·mL-1 with a low limit of detection (LOD, 0.37 pg·mL-1, S/N = 3). The developed immunosensor exhibited high selectivity and good stability. ECL determination of CEA in fetal bovine serum was achieved.

Hydrodynamics and mass transport in an anodic oxidation reactor: Influence of gas evolution and flow path through mesh electrodes

Removal of organic compounds by anodic oxidation requires a sufficiently high rate of mass transport of target compounds to the electrode surface. Since anodic oxidation is often accelerated by the formation of hydroxyl radicals from water oxidation at high anodic potential, the role of oxygen/hydrogen evolution reactions was investigated. Residence time distributions showed that formation of bubbles in zones where fluid velocity was minimal, allowed for strongly improving global hydrodynamics in the reactor. The role of bubbles was also discussed by comparing mass transport coefficients obtained from the limiting current technique to values obtained from kinetics of COD removal during treatment of a model pollutant (phenol). The use of mesh electrodes (with liquid flowing through the electrode) further promoted convection and mass transport of organic compounds compared to plates. However, large bubbles generated at plate electrodes also allowed for convection enhancement in the vicinity of surface of plate electrodes. In both cases, an adverse effect from bubble adhesion was observed because of the decrease in the active surface of electrodes. The mass transport coefficient obtained with the limiting current technique using mesh electrodes was 0.69 10−3 cm/s at 10.8 L/h with a mean velocity of electrolyte past the mesh surface (u¯mesh) of 0.37 cm/s. It decreased to 0.58 10−3 cm/s during the treatment of phenol at the same flow and reached 0.75 10−3 cm/s when increasing the flow to 32.4 L/h. By taking into consideration gas evolution at the surface of electrodes, this study allowed for accurate calibration of an advective – dispersive model with reaction that could be used for sizing such reactors according to the intended application.Abbreviations: Ae, the volumetric surface area (ratio between the geometric volume and the active surface area of the mesh electrodes) (cm−1); CA, aeration by a floor diffuser of fine bubbles and no current at the electrodes; CEP, polarization of the electrodes with a current intensity and no aeration; CW, no electrode polarization and no aeration; COD, chemical oxygen demand (mgO2 L−1);Di, diffusion coefficient of specie i (m2/s); D, dispersion coefficient (cm2 min−1); E(θ), residence time distribution function; EC, electrical energy consumption (kWh gCOD−1);F, Faraday constant (96485C mol−1); HER, hydrogen evolution reaction; IOA, index of agreement;km, mass transport coefficient (m/s); MCE, mineralization current efficiency; ME, model efficiency; OER, oxygen evolution reaction; OH, hydroxyl radical;Ql, liquid flow rate (L/h); rAO: anodic oxidation rate (mol/m−3 s−1); RTD: residence time distribution; ts¯: mean residence time or first moment order; u¯: mean flow velocity (m/s); VT: total volume (L); σ2: variance or second moment order; γ: skewness factor or third moment order; τ: residence time; μ: order moment.

Concept of Utilizing Ionic Liquids for the Co‐Electroreduction of Carbon Dioxide and Nitrogen‐Containing Compounds

AbstractFormation of C−N bonds through the electrochemical utilization of CO2 and nitrogen containing compounds (N‐compounds) is appealing for the purpose of converting waste and readily available sources or pollutants into value added chemicals at ambient conditions. Existing research predominantly explores these electrochemical reactions independently, often in aqueous electrolytes, leading to challenges associated with competitive hydrogen evolution reaction (HER), low product selectivity, and yield. Functional electrolytes such as those containing ionic liquids (ILs) present selective solubility to the solute reactants and present unique interactions with the electrode surface that can suppress the undesired side reactions such as HER while simultaneously co‐catalyzing the conversion of CO2 and N‐compounds such as N2, NO, NO2, and NO3. In this concept paper, we discuss how the microenvironment enabled by ILs can be leveraged to stabilize reaction intermediates at the electrode‐electrolyte interface, thereby promoting C−N bond formation on an active electrode surface at reduced overpotential, with the case study of CO2 and N‐compounds co‐catalysis to generate urea.

Understanding Performance Limitation of Liquid Alkaline Water Electrolyzers

Liquid alkaline water electrolyzers (LAWEs), being the most commercially mature electrolysis technology, play a pivotal role in large-scale hydrogen production. However, LAWEs suffer from low operational efficiency, primarily due to un-optimized electrode structure and chemical compositions. Thus, we investigated how various electrode configurations could impact LAWE performance. Our results show that Ni felt electrodes outperform the conventional Ni foam thanks to improved electrochemical active surface area (ECSA) and preferred electrode surface structure that minimizes the micro-gaps in between the electrode and separator. By comparing the stainless steel (SS) felt electrodes with Ni felt electrodes, SS not only shows better oxygen evolution reaction activity but also improved hydrogen evolution reaction activity, which is less studied in the literature. We also show that a bilayer structure with small pore radius facing the separator could further improve LAWE performance by further optimizing interfacial contact between electrode and separator. These findings enable LAWEs to sustain 2 A cm−2 at 2.2 V and operate steadily at 1 A cm−2 for nearly 600 h with negligible performance decay. Our studies establish criteria for selecting electrodes to achieve high-performance LAWE and, in turn, expedite the adoption of LAWEs in hydrogen production and the transition towards low-carbon economies.

Efficient oxidation of hydrazine over electrochemically activated glassy carbon electrode surface: Kinetics and sensing performance

Hazardous chemical hydrazine (HZ) can enter the body through the skin and harm the kidneys and liver. Consequently, it is imperative to accurately determine HZ concentrations in samples. One significant challenge in the direct and sensitive detection of analytes is the higher oxidation overpotential and inferior voltammetric response over the conventional bare electrode surface, attributed to the passivation of the electrode surface. To address this issue, we electrochemically activated (oxidized) a pristine glassy carbon electrode (GCE) in a mild acidic medium. The activated GCE demonstrated improved HZ oxidation efficiency. The activated GCE exhibited a distinct redox pair in 0.1 M H2SO4 because of the growth of C=O groups onto the electrode surface during electrochemical oxidation. We characterized the GCE surface before and after the functionalization using electrochemical processes, Scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS). This activated electrode surface was utilized for electrochemical HZ oxidation in an alkaline medium, revealing enhanced electrochemical performance compared to the pristine GCE regarding HZ oxidation following conventional Butler-Volmer kinetics. Thorough electrochemical analyses and characterizations of the sensor were performed utilizing techniques such as Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS), Open Circuit Potential (OCP), Chronoamperometry (i-t curve), and Differential Pulse Voltammetry (DPV). The correlation between the current response and HZ concentration displayed an extensive linear dynamic range (LDR) spanning from 6 to 1000 μM, boasting a limit of detection (LOD) at 0.48 μM. The sensor's sensitivity was determined to be 3.1 μA μM−1 cm−2. The proposed activated GCE effectively reduces HZ oxidation overpotentials, thereby enhancing its potential application as an anode in direct hydrazine fuel cells.

Electroflocculation kinetics of humic acid removal from boiler make-up water using Al-base electrodes

Many coal-fired power plants have undergone a "heating transformation." This transformation measure significantly increases the boiler make-up water required by the power plant, and the make-up water source contains humic acid (HA) organic matter. HA will cause problems such as corrosion、scaling of thermal equipment and increaseing the difficulty of water treatment. The kinetics of electroflocculation were investigated in this study using an experimental device designed to treat HA from boiler make-up water, which is made of plexiglass and has a capacity of 1.2 L. The alloy plates are placed parallel to each other and perpendicular to the horizontal plane as the anode and cathode and are connected to the DC power supply through a wire. Three parameters were investigated: current density, initial pH, and electrode distance. The experimental results show that electroflocculation has a better removal effect on HA. The reaction rate constants of the three electrodes (Al–Zn–In, 6061 alloy, and Al) were 0.07994, 0.04282, and 0.03174 min−1. When the pH was 5, the current density was 100A·m−2, and the spacing between the electrodes was 3 cm, the highest rate constant of 0.10249 min−1 was observed for Al–Zn–In, and the removal rate of HA was 93.3% in 30 min. The SEM and EDS analyses were performed on the electrode and precipitated before and after electroflocculation. The doping of Al–Zn–In with In and Zn helps maintain the electrode surface's activation state during electroflocculation. The electroflocculation effect and anti-passivation ability of the three metals are Al–Zn–In＞6061 alloy＞Al. Al–Zn–In is expected to replace aluminum plates due to its resistance to passivation and superior electroflocculation effect.

Challenging electroanalytical method for the determination of mirabegron in biological samples and pharmaceutical formulations

A simple, economic, sensitive, and time-saving differential pulse voltammetric (DPV) procedure using nanostructured zinc oxide modified carbon paste electrode (nano ZnO-CPE) in conjunction with an anionic surfactant sodium dodecyl sulfate (SDS) was developed for ultra- sensitive detection of mirabegron (MIR), the most prescribed pharmaceutical drug in treatment of overactive bladder (OAB). The use of nanostructured zinc oxide CPE modifier increased the electrode active surface area as well as improved the process of electron transfer, also it was found that at optimal conditions MIR electrochemical process was both irreversible and diffusion-regulated. The morphological characterization of the fabricated electrode was performed using field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectroscopy (EDX). MIR voltammetric behavior was investigated using Nano ZnO-CPE in different content and electrode compositions. Therefore, ultra-sensitive results were attained with a linearity range of (0.55 to 100.20 ng ml−1) and a low limit of detection (LOD) of 0.51 ng ml−1 and limit of quantification (LOQ) of 1.54 ng ml−1 in a 0.04 M Britton-Robinson (BR) buffer at an adjusted pH of 6.0 with scan rate 100 mV s−1. Furthermore, the proposed approach was successful in measuring MIR with acceptable percentage recoveries (99.81–100.11 %) in pharmaceutical dosage form and varying concentration ranges in biological samples (99.74–100.35 %). The proposed method has been validated using ICH criteria and proven to be accurate and repeatable.

First Acyclovir Determination Procedure via Electrochemically Activated Screen-Printed Carbon Electrode Coupled with Well-Conductive Base Electrolyte.

In this work, a new voltammetric procedure for acyclovir (ACY) trace-level determination has been described. For this purpose, an electrochemically activated screen-printed carbon electrode (aSPCE) coupled with well-conductive electrolyte (CH3COONH4, CH3COOH and NH4Cl) was used for the first time. A commercially available SPCE sensor was electrochemically activated by conducting cyclic voltammetry (CV) scans in 0.1 mol L-1 NaOH solution and rinsed with deionized water before a series of measurements were taken. This treatment reduced the charge transfer resistance, increased the electrode active surface area and improved the kinetics of the electron transfer. The activation step and high conductivity of supporting electrolyte significantly improved the sensitivity of the procedure. The newly developed differential-pulse adsorptive stripping voltammetry (DPAdSV) procedure is characterized by having the lowest limit of detection among all voltammetric procedures currently described in the literature (0.12 nmol L-1), a wide linear range of the calibration curve (0.5-50.0 and 50.0-1000.0 nmol L-1) as well as extremely high sensitivity (90.24 nA nmol L-1) and was successfully applied in the determination of acyclovir in commercially available pharmaceuticals.

Electrochemical Sensing with Spatially Patterned Pt Octahedra Electrodes

AbstractLocally controlling the position of electrodes in 3D can open new avenues to collect electrochemical signals in complex sensing environments. Implementing such electrodes via an electrical network requires advanced fabrication approaches. This work uses corner lithography and Pt ALD to produce electrochemical 3D electrodes. The approach allows the fabrication of (sub)micrometer size Pt octahedra electrodes spatially supported over 3D fractal‐like structures. As a proof of concept, electrochemical sensing of ferrocyanide in biofouling environments, e.g., bovine serum albumin (BSA) and Pseudomonas aeruginosa (P. aeruginosa), is assessed. Differences between before and after BSA addition show a reduction in the active electrode surface area (ΔAeff) ≈49% ± 7% for the flat electrode. In comparison, a ΔAeff reduction of 25% ± 2% for the 3D electrode has been found. The results are accompanied by a 24% ± 16% decrease in peak current for the flat Pt substrate and a 14% ± 5% decrease in peak current for the 3D electrode 24 h after adding BSA. In the case of P. aeruginosa, the 3D electrode retains electrochemical signals, while the flat electrode does not. The results demonstrate that the 3D Pt electrodes are more stable than their flat counterparts under biofouling conditions.

Electrochemical reconstruction of non-noble metal-based heterostructure nanorod arrays electrodes for highly stable anion exchange membrane seawater electrolysis

Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis. However, the harsh electrochemical environment of seawater, particularly the presence of aggressive Cl−, has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions, thus restricting seawater electrolyzer lifetime. Herein, hierarchical structure (Ni,Fe)O(OH)@NiCoS nanorod arrays (NAs) catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation. The hierarchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction (OER) and generated sulfate gradient layers to repulsive aggressive Cl−. The fabricated heterostructure and vacancies of (Ni,Fe)O(OH) tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphous γ-NiFeOOH for promoting OER. Furthermore, through operando electrochemistry techniques, we found that the γ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl− corrosion enabled by stabilizing the adsorption of OH* intermediates, making it one of the best OER catalysts in the seawater medium reported to date. Consequently, these catalysts can deliver current densities of 100 and 500 mA cm−2 for boosting OER at minimal overpotentials of 245 and 316 mV, respectively, and thus prevent chloride ion oxidation simultaneously. Impressively, a highly stable anion exchange membrane (AEM) seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100 μV h−1 at constant industrial current densities of 400 and 600 mA cm−2 over 300 h, which exhibits a promising future for the non-precious and stable AEMWE in the direct seawater electrolysis industry.

Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111).

The proton-coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long-standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR-PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well-defined Pt(111). We unveil a dual-cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt-O and Pt-OH overlayers and ii) the competition between inner- and outer-sphere PCET steps. The cation-dependent transition from Pt-O to Pt-OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.

Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111)**

AbstractThe proton‐coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long‐standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR‐PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well‐defined Pt(111). We unveil a dual‐cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt−O and Pt−OH overlayers and ii) the competition between inner‐ and outer‐sphere PCET steps. The cation‐dependent transition from Pt−O to Pt−OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.

SEI growth on Lithium metal anodes in solid-state batteries quantified with coulometric titration time analysis

Lithium-metal batteries with a solid electrolyte separator are promising for advanced battery applications, however, most electrolytes show parasitic side reactions at the low potential of lithium metal. Therefore, it is essential to understand how much (and how fast) charge is consumed in these parasitic reactions. In this study, a new electrochemical method is presented for the characterization of electrolyte side reactions occurring on active metal electrode surfaces. The viability of this new method is demonstrated in a so-called anode-free stainless steel ∣ Li6PS5Cl ∣ Li cell. The method also holds promise for investigating dendritic lithium growth (and dead lithium formation), as well as for analyzing various electrolytes and current collectors. The experimental setup allows easy electrode removal for post-mortem analysis, and the SEI’s heterogeneous/layered microstructure is revealed through complementary analytical techniques. We expect this method to become a valuable tool in the future for solid-state lithium metal batteries and potentially other cell chemistries.

Voltammetric Sensing of Nifedipine Using a Glassy Carbon Electrode Modified with Carbon Nanofibers and Gold Nanoparticles.

Nifedipine, a widely utilized medication, plays a crucial role in managing blood pressure in humans. Due to its global prevalence and extensive usage, close monitoring is necessary to address this widespread concern effectively. Therefore, the development of an electrochemical sensor based on a glassy carbon electrode modified with carbon nanofibers and gold nanoparticles in a Nafion® film was performed, resulting in an active electrode surface for oxidation of the nifedipine molecule. This was applied, together with a voltammetric methodology, for the analysis of nifedipine in biological and environmental samples, presenting a linear concentration range from 0.020 to 2.5 × 10-6 µmol L-1 with a limit of detection 2.8 nmol L-1. In addition, it presented a good recovery analysis in the complexity of the samples, a low deviation in the presence of interfering potentials, and good repeatability between measurements.

Electrochemical Determination of Ascorbic Acid by Mechanically Alloyed Super Duplex Stainless Steel Powders

SAF-2507 super duplex stainless steel powders (SDSS) were prepared using a high-energy planetary ball milling process. The X-ray diffraction (XRD) shows peak broadening after 20 h of ball milling and revealed a phase transformation resulting in a two-phase alloy mixture containing nearly equal amounts of ferrite (α) and austenite (γ). After 20 h of ball milling the particle size was reduced to ~201 nm. Scanning electron microscope (SEM) micrographs showed small-size irregular grains with an average particle size ranging from 5–7 µm. The high-resolution transmission microscope (HRTEM) analysis confirmed the presence of nanocrystalline particles with sizes ranging from 10 to 50 nm. The presence of ferrite phase is visible in the corresponding diffraction pattern as well. In this paper, we have discussed the electrochemical sensor application of mechanically alloyed nano-structured duplex stainless steel powders. The fabricated 4 mg duplex stainless steel modified carbon paste electrode (SDSS-MCPE) has shown excellent current sensitivity in comparison with 2, 6, 8, and 10 mg SDSS-MCPEs during the detection of ascorbic acid (AA) in a phosphate buffer solution with a pH of 6.8. The calculated electrode active surface area of SDSS-MCPE was found to be almost two times larger than the surface area of the bare carbon paste electrode (BCPE). The limit of detection (LD) and limit of quantification (LQ) were found to be 0.206 × 10−8 M and 0.688 × 10−8 M, respectively, for the fabricated 4 mg SDSS-MCPE.

Synthesis of N-acylated pyrazolines: Spectroscopic, crystallographic, Hirshfeld Surface, lead sensing and theoretical studies

N-Acylated-2-pyrazolines (NA2Pyr) were synthesized from chalcone and hydrazine hydrate under one pot cyclocondensation in the presence of propionic acid and trifluoroacetic acid respectively. The structures were determined using FT-IR, 1H NMR, 13C NMR spectral analyses, as well as single crystal diffraction study (Sc-XRD). An effective metal ion sensor (Lead ion) with a flat glassy carbon electrode (GCE) was produced for prospective use by coupling a conducting coating binder (PEDOT:PSS) with a thin-layer NA2Pyr modified electrode (NA2Pyr/GCE). Linear sweep voltammetry was used to detect lead (Pb2+) ions in phosphate aqueous phase. The sensitivity (11,867 uAnM−1cm−2) of the chemical sensor probe was measured utilizing the calibration curve slope and the adjusted electrode active surface area. The linear dynamic range (LDR: 0.01 nM to 10.0 mM) was computed using the calibration plot's maximal linearity line. The detection limit (0.008 nM) was calculated by including 3σ/m (where σ is the standard deviation of the blank response and m is the slope of the calibration curve). The novel electrochemical method is dependable and effective technique for detecting heavy metal ions as a selective lead-sensor for the protection of large-scale medical, biochemical, and environmental fields. Density functional theory (TD-DFT/B3LYP/6-311++G(d,p) was used to computed FMO computations and further study using the optimized geometric parameters of the ground state molecules. According to the predicted energies for HOMO and LUMO, in which the charge of molecule is conveyed, and MEP map, the chemically reactive zone suitable for drug action was identified. The Electron Localization Function (ELF), Non-Bonding Orbitals, Excitation Energies, AIM Charges, and Fukui Functions are also calculated. The docking study contributed to the analysis of EGFR protein binding.

Natural and Forced Convection in Multi-Phasic Electrochemical Systems

Multi-phasic electrochemical systems such as electrolyzers or metal-air batteries are intimately linked to energy transition and are at the heart of new scientific advances and modern industrial development. The presence of gas phases, inherent to the processes, directly impacts the performance and stability of the systems. In this study, we propose different ways to improve the dynamics of bubble evacuation, through forced convection (flow systems), and natural convection (electrode design and cell geometry). By analyzing the links between the electrochemical kinetics and active surface electrode variations, we show that forced convection is an excellent way to decrease the overall energy cost and reduce the harmful impact of gas bubbles. Regarding natural evacuation, adapted electrode or cell designs also allow to improve performances, without adding external hydraulic circuit.

Sulfonate-Grafted Metal–Organic Framework─A Porous Alternative to Nafion for Electrochemical Sensors

Nafion, a polymer containing negatively charged sulfonate groups, is commonly used as a thin film cast on the electrode to adjust the selectivity of complicated electrochemical reactions involving charged reactants or analytes in the electrochemical sensing and electrolytic systems. Herein, a highly porous and chemically stable metal–organic framework (MOF) with enriched sulfonate groups in its pores is synthesized by performing the postsynthetic immobilization of the sulfonate-based ligand within a zirconium-based MOF, MOF-808, and the resulting sulfonate-grafted MOF (SO3-MOF-808) is proposed as a “porous Nafion”─an appealing alternative to the conventional Nafion coating for modulating the selectivity of electrochemical reactions. As a demonstration, the electrochemical sensing of dopamine (DA), which usually suffers from interference caused by the oxidation of the coexisting negatively charged ascorbic acid (AA) and uric acid (UA), is implemented. With the use of the SO3-MOF-808 thin film deposited on the active electrode surface, both the current signal for DA oxidation and the selectivity toward the oxidation of DA against those of AA and UA remarkably outperform those achieved by the Nafion thin film with an optimized film thickness. Findings here suggest the new role of such sulfonate-grafted MOFs as an advanced alternative to Nafion in a range of electrochemical sensing systems and other complicated electrochemical reactions.

Screen-printed gold electrode for ultrasensitive voltammetric determination of the antipsychotic drug thioridazine

A highly sensitive, fast and simple analytical procedure for analysis of the antypsychotic drug thioridazine (TDZ) using an original screen-printed gold electrode (SPAuE) was developed. The cyclic voltammetry, scanning electron microscopy, electrochemical impedance and energy-dispersive X-ray spectroscopy were used for the SPAuE characterization. The results showed the advantage of the commercially available SPAuE in terms of working electrode active surface and the efficiency of kinetics of electron transfer compare to unmodified and ex situ modified gold film screen-printed carbon electrode. Moreover, the results displayed that an irreversible, adsorption-controlled oxidation process of TDZ in phosphate buffered saline of pH 2.6 is connected with the strong affinity of sulfur atoms for gold. The SPAuE allows for a much lower detection limit (2.9 × 10−12 M) than in the case of other electrochemical sensors used for TDZ analysis. The measurements results were validated by official and standard addition methods.

Electrochemical Gelation of Metal Chalcogenide Quantum Dots: Applications in Gas Sensing and Photocatalysis.

ConspectusMetal chalcogenide quantum dots (QDs) are prized for their unique and functional properties, associated with both intrinsic (quantum confinement) and extrinsic (high surface area) effects, as dictated by their size, shape, and surface characteristics. Thus, they have considerable promise for diverse applications, including energy conversion (thermoelectrics and photovoltaics), photocatalysis, and sensing. QD gels are macroscopic porous structures consisting of interconnected QDs and pore networks in which the pores may be filled with solvent (i.e., wet gels) or air (i.e., aerogels). QD gels are unique because they can be prepared as macroscale objects while fully retaining the size-specific quantum-confined properties of the initial QD building blocks. The extensive porosity of the gels also ensures that each QD in the gel network is accessible to the ambient, leading to high performance in applications that require high surface areas, such as (photo)catalysis and sensing.Metal chalcogenide QD gels are conventionally prepared by chemical approaches. We recently expanded the toolbox for QD gel synthesis by developing electrochemical gelation methods. Relative to conventional chemical oxidation approaches, electrochemical assembly of QDs (1) enables the use of two additional levers for tuning the QD assembly process and gel structure: electrode material and potential, and (2) allows direct gel formation on device substrates to simplify device fabrication and improve reproducibility. We have discovered two distinct electrochemical gelation methods, each of which enables the direct writing of gels on an active electrode surface or the formation of free-standing monoliths. Oxidative electrogelation of QDs leads to assemblies bridged by dichalcogenide (covalent) linkers, whereas metal-mediated electrogelation proceeds via electrodissolution of active metal electrodes to produce free ions that link QDs by binding to pendant carboxylate functionalities on surface ligands (non-covalent linkers). We further demonstrated that the electrogel composition produced from the covalent assembly could be modified by controlled ion exchange to form single-ion decorated bimetallic QD gels, a new category of materials. The QD gels exhibit unprecedented performance for NO2 gas sensing and unique photocatalytic reactivities (e.g., the "cyano dance" isomerization and the reductive ring-opening arylation). The chemistry unveiled during the development of electrochemical gelation pathways for QDs and their post-modification has broad implications for guiding the design of new nanoparticle assembly strategies and QD gel-based gas sensors and catalysts.