Heterogeneous Electron Transfer Rate Research Articles

Influence of CO2 laser beam modelling on electronic and electrochemical properties of paper-based laser-induced graphene for disposable pH electrochemical sensors

Laser-induced graphene (LIG) allows for the fabrication of cost-effective, flexible electrodes on a multitude of recyclable and sustainable substrates, for implementation within electrochemical biosensors. This work expands on current LIG research, by experimentally modeling the effects of several CO2 laser irradiation variables towards resulting conductive and electrochemical properties of paper-derived LIG. Instead of relying on the established paradigm of manipulating power and scan speed of the laser irradiation process for optimized outcomes, modeling of underlying laser operation principles for pulse modulation, regarding pulse repetition frequencies, pulse duration and defocus are presented as the key aspects dominating graphitization processes of materials. This approach shows that graphitization is dominated by appropriate pulse durations, dictating the time the substrate is exposed to each laser pulse, with laser fluence and irradiation defocus influencing the resulting conductive properties, with sheet resistances as low as 14 Ω sq−1. Similarly, fabrication settings controlled by these parameters have a direct influence on the properties of LIG-based electrochemical three-electrode cells, with optimized fabrication settings reaching electrochemically active surface area as high as 35 mm2 and heterogeneous electron transfer rates of 3.4 × 10−3 cm.s−1. As a proof-of-concept, the production of environmentally friendly, accessible, and biocompatible pH sensors is demonstrated, using two modification approaches, employing riboflavin and polyaniline as pH-sensitive elements.

Electrochemical Mechanisms of Copper Bipyridine Complexes in Dichloromethane and Water

Voltammetric mechanisms for copper bipyridine complexes are evaluated for Cu(bpy)3(PF6)2 in dichloromethane (DCM), Cu(bpy)3(ClO4)2 in water, and copper bipyridine complexes formed in situ from a stoichiometric 1:3 mix of Cu(II) and bpy in water. The mechanism for Cu(bpy)3(PF6)2 in aprotic DCM is a simple irreversible (slow) heterogeneous electron transfer, , with a standard heterogeneous electron transfer rate of 6 × 10−4 cm s−1. For Cu(bpy)3(ClO4)2 in water near pH 6, the mechanism is a six species square scheme, with multiple chemical and electrochemical steps. Voltammetric morphologies for Cu(bpy)3(PF6)2 in DCM and Cu(bpy)3(ClO4)2 in water were evaluated by established diagnostics and modeled with digital simulations. Established diagnostics underrepresent the complexity of copper bipyridines in water. For the complexes formed in situ, the stoichiometric ratio is insufficient to form only Cu(bpy)3 2+, so an equilibrium model that characterizes speciation at given pH and electrode potentials is used. Solvent, pH, and speciation impact the observed voltammetry of copper bipyridine complexes.

Disposable Pencil Lead as an Electrochemical Transducer for Monitoring Catechol in River and Tap Water

A cheap and disposable pencil graphite electrode (PGE) was developed by the incorporation of amine groups (Am-PGE-1). A further improvement in the performance was observed when the aminated electrode (Am-PGE-1) was activated by applying a negative potential scan (Am-PGE-2). The electrochemical transport properties were evaluated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The Nyquist plot showed a reduced charge transfer resistance value of 24.3 Ω for Am-PGE-2, while it was 95.1 Ω for bare PGE. Thus, Am-PGE-2 was used as a sensing platform for the detection of catechol. It was found that the electrochemical response of catechol oxidation at Am-PGE-2 was twice than the current obtained for bare PGE. Additionally, the effect of pH of the supporting electrolyte and reaction kinetic were studied. The heterogeneous electron transfer rate constant was calculated to be 0.01 s−1. Moreover, CV study revealed that the redox reaction of catechol was a quasi-reversible and diffusion-controlled process. The square wave voltammetry (SWV) technique was applied for the quantitative determination of catechol. The peak current showed a linear dependency on the concentration of catechol from 3 to 150 µM. Furthermore, the analyte could be detected as low as 3.86 µM. Likewise, the sensor demonstrates a good selectivity towards the target analyte than the other possible interfering molecules or ions. Aiming to examine practical applicability, real samples, such as river and household tap water, were tested by using the proposed transducer, and the satisfactory recoveries demonstrate the effectiveness of Am-PGE-2 in real life applications.

Theory for Heterogeneous Electron Transfer Kinetics on Nanocorrugated Atomic Stepped Metal Electrodes

We develop a novel mean-field theoretical approach for the outer-sphere heterogeneous electron transfer (OS-HET) rate constant at an atomically stepped nanocorrugated metal surface. Theory accounts for the contributions from the nature of the metal, local curvature of the nanocorrugated atomic step, the density of atomic steps and kinks, dipolar solvents, and the frontier molecular orbital of electroactive molecules. Our theoretical approach develops a novel model for the free energy of activation obtained using the alignment of the Fermi energy level in the metal with one of the frontier molecular orbitals of the electroactive species. The activation free energy is obtained as a product of a modified work function (WF) and the fractional electronic charge of activation for the alignment of levels. Metal surface local curvatures at atomic steps are modeled as a hyperbolic tangent functional with a random nanocorrugated step edge. The influence of step density and edge fluctuations (or kinks) on the activation free energy is included through the surface average mean curvature and the mean-square gradient dependent modified WF. The theoretical results highlight the step density-dependent nonmonotonic variation in WF, fractional electronic charge, and activation free energy. The increase in step density shifts the Fermi energy level toward LUMO and away from HOMO energy levels. This causes the reduced (for the LUMO) and enhanced (for the HOMO) activation free energy for ET kinetics compared to the basal plane. The dichotomy in the OS-HET kinetics at the atomically stepped metal results in anomalous enhancement and suppression for the LUMO and HOMO, respectively. The strong influence of kinks along the step edge on the HET rate constant is predicted up to 6 decades (compared to the basal surface of Pt metal). Finally, theory shows agreement with the reported experimental data of WF and exchange current density for single crystal Pt electrodes.

Electrochemistry and Mass Transport of Ytterbium(III) in Bis(trifluoromethylsulfonyl)imide-Based Room-Temperature Ionic Liquids: Effects of Temperature, Viscosity, and Electrode Materials

Cyclic staircase voltammetry, rotating disk electrode voltammetry, controlled potential coulometry, and electrochemical impedance spectroscopy were used to probe the electrochemistry and mass transport of Yb3+ in the six room temperature ionic liquids based on the bis(trifluoromethylsulfonyl)imide (Tf2N−) anion with, 1-(1-butyl)−3-methylimidazolium (BuMeIm+), 1-(1-butyl)−1-methylpyrrolidinium (BuMePyro+), 1-(1-butyl)pyridinium (BuPy+), 1-butyltrimethylammonium (BuMe3N+), 1-ethyl-3-methylimidazolium (EtMeIm+), and tri(1-butyl)methylammonium (Bu3MeN+) cations. These investigations were carried out at glassy carbon as well as polycrystalline gold, platinum, and tungsten electrodes. The heterogeneous electron transfer rate of the quasireversible Yb3+/2+ redox couple was found to depend strongly on the electrode materials with the fastest rate observed at gold and the slowest rate found at tungsten, but was independent of the physicochemical properties of the various ionic liquids, in particular, the absolute viscosity. However, the mass transport of Yb3+ was dependent on the viscosity, and the temperature dependence of the diffusion coefficients was well represented by a Vogel-Tammann-Fulcher type expression for glass-forming ionic liquids. Analysis of the diffusion coefficient data with the Stokes-Einstein equation indicated that the solvodynamic radius of the diffusing Yb3+ was constant and independent of the structure and properties of the ionic liquid cations. The solvodynamic radius of Yb3+ was estimated from the “stick model” for the Stokes-Einstein equation. Application of the Random Closest Packing (RCP) model for spheres in consideration of the solvodynamic radius of the diffusing Yb3+ and the ionic radii of Yb3+ and Tf2N−, indicated that the former must diffuse in association with ∼5–6 of the anions.

Room-Temperature Ionic Liquid Cation Effects on the Structure and Stability of Anionic Lanthanide Complexes.

Room-temperature ionic liquids (RTILs) are a subset of molten salts that are liquids at room temperature and may offer an elegant, low-temperature route to predicting the properties of solvated metal complexes in their high-temperature analogues. This work studied the chemistry of chloride anion-containing RTILs to determine their similarity to inorganic molten chloride salts. The behaviors of complexes of Mn, Nd, and Eu were evaluated in a variety of chloride RTILs by absorption spectrophotometry and electrochemistry to elucidate trends in cation effects on the coordination geometry and redox properties of the solvated species. Spectrophotometric data indicated the metals are present as anionic complex (e.g., MnCl42- and NdCl63-) analogous to those observed in molten chloride salts. Strongly polarizing, charge-dense RTIL cations induced distortions to the symmetry of these complexes, resulting in lower oscillator strengths and red-shifted energies for the observed transitions. Cyclic voltammetry experiments were used to characterize the Eu(III/II) redox couple producing diffusion coefficients on the order of 10-8 cm2 s-1 and heterogeneous electron transfer rate constants ranging between 6 × 10-5 and 2 × 10-4 cm s-1. The E1/2 potentials for Eu(III/II) were also found to shift positively with increasing cation polarization power, stabilizing the Eu(II) oxidation state by removing electron density from the metal center over chloride bond networks. Both the optical spectrophotometry and electrochemistry results suggest that the polarization strength of an RTIL cation plays a major role in the geometry and stability of a metal complex.

Voltammetric Evidence of Proton Transport through the Sidewalls of Single-Walled Carbon Nanotubes.

Understanding ion transport in solid materials is crucial in the design of electrochemical devices. Of particular interest in recent years is the study of ion transport across 2-dimensional, atomically thin crystals. In this contribution, we describe the use of a host-guest hybrid redox material based on polyoxometalates (POMs) encapsulated within the internal cavities of single-walled carbon nanotubes (SWNTs) as a model system for exploring ion transport across atomically thin structures. The nanotube sidewall creates a barrier between the redox-active molecules and bulk electrolytes, which can be probed by addressing the redox states of the POMs electrochemically. The electrochemical properties of the {POM}@SWNT system are strongly linked to the nature of the cation in the supporting electrolyte. While acidic electrolytes facilitate rapid, exhaustive, reversible electron transfer and stability during redox cycling, alkaline-salt electrolytes significantly limit redox switching of the encapsulated species. By "plugging" the {POM}@SWNT material with C60-fullerenes, we demonstrate that the primary mode of charge balancing is proton transport through the graphenic lattice of the SWNT sidewalls. Kinetic analysis reveals little kinetic isotope effect on the standard heterogeneous electron transfer rate constant, suggesting that ion transport through the sidewalls is not rate-limiting in our system. The unique capacity of protons and deuterons to travel through graphenic layers unlocks the redox chemistry of nanoconfined redox materials, with significant implications for the use of carbon-coated materials in applications ranging from electrocatalysis to energy storage and beyond.

Semi-microscopic Theory for the Current Rectification Phenomenon in Nanogap Molecular Devices.

A semi-microscopic theory is developed for heterogeneous electron transfer (HET) kinetics based on the energy level alignment approach at self-assembled monolayer (SAM) covered metal electrodes. Theory provides the electronic and molecular property-dependent equations for the HET rate constant (k0) and the transfer coefficient (α) for potential. k0 is formulated using the activation free energy as a product of the SAM covered metal work function (WF) and fractional electronic charge exchanged at the transition state (attained through the alignment of the frontier molecular orbital (FMO) energy level of the electroactive group with the WF of metal). k0 is a function of the metal jellium electronic screening length and dielectric and of the molecular self-assembly (through its dipole moment, size, and packing density) and the FMO energies of electroactive groups. The operative potential at the transition state is governed by α, which is a function of molecular spacer length and characteristic electronic-dipolar coupling length. The current rectification phenomenon in nanogap molecular devices is theoretically analyzed using equations for k0 and α for SAM covered source and drain electrodes. Theory unravels the LUMO or HOMO dichotomy for a given metal: (i) for the HOMO assisted ET, the metal with a high WF has a high current rectification ratio (RR), while (ii) for the LUMO assisted ET, the metal with a low WF has a high current RR in asymmetrical devices. Theory predicts the reversal in current rectification by altering the dipole moment of the anchoring molecule, the HOMO/LUMO energy of the electroactive groups, and the nature of the metal. Finally, theory shows qualitative and quantitative coherence with the reported experimental current-potential response of molecular device.

Probing Redox Properties of Extreme Concentrations Relevant for Nonaqueous Redox-Flow Batteries

Redox-flow batteries are an emerging energy storage technology that can pair with intermittent renewable energy technologies. There remains a need, however, to understand physicochemical relationships among the solvent, electrolyte salt, and redox-active molecules that comprise catholyte and anolyte solutions. To examine this relationship, we detail a systematic study wherein the concentrations of the redox-active molecule 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and TBAPF6 electrolyte salts are varied over concentrations of 1 mM to over 1000 mM in acetonitrile. Three series were investigated: (1) varying the concentration of TEMPO while holding the concentration of TBAPF6 constant, (2) varying the concentration of TBAPF6 while holding the concentration of TEMPO constant, and (3) varying both the concentration of TEMPO and TBAPF6 with a 5:1 TBAPF6:TEMPO ratio. Cyclic voltammetry data from macro- and microelectrodes were used to quantify diffusion coefficients and heterogeneous electron transfer rates, and these metrics were connected to the conductivity and viscosity to develop clear trends over the entire concentration range. Fundamental chemical interactions that lead to changes in physical properties were implicated via vibrational spectroscopy and molecular dynamics (MD) simulations. Trends in conductivity and viscosity for systems were inversely related and correlated to trends in diffusion coefficients and heterogeneous electron transfer rates. Intuitively, faster diffusion and electron-transfer rates occurred with lower TEMPO concentrations and higher TBAPF6 concentrations, with the majority of conditions falling in the general proximity of literature values (k0 = 0.1–0.5 cm/s, D ≈ (2.0–4.0) × 10–5 cm2/s). At the highest TBAPF6 concentrations, vibrational spectroscopy and MD simulations show that intermolecular interactions were more nuanced, and solvation and ion-pairing effects begin to influence electrochemical and physical properties. This functional approach including electrochemical and physical characterization paired with MD simulations provides a template for methodically studying systems for redox flow battery applications.

Electrochemistry at Back-Gated, Ultrathin ZnO Electrodes: Field-Effect Modulation of Heterogeneous Electron Transfer Rate Constants by 30× with Enhanced Gate Capacitance.

We report steady-state voltammetry of outer-sphere redox species at back-gated ultrathin ZnO working electrodes in order to determine electron transfer rate constants kET as a function of independently controlled gate bias, VG. We demonstrate that kET can be modulated as much as 30-fold by application of VG ≤ 8 V. The key to this demonstration was integrating the ultrathin (5 nm) ZnO on a high dielectric constant (k) insulator, HfO2 (30 nm), which was grown on a Pd metal gate. The high-k HfO2 dramatically decreased the required VG values and increased the gate-induced charge in ZnO compared to previous studies. Importantly, the enhanced gating power of the Pd/HfO2/ZnO stack meant it was possible to observe a nonmonotonic dependence of kET on VG, which reflects the inherent density of redox acceptor states in solution. This work adds to the growing body of literature demonstrating that electrochemical kinetics (i.e., rate constants and overpotentials) at ultrathin working electrodes can be tuned by VG, independent of the conventional electrochemical working electrode potential.

Effect of adsorption of pyocyanin on the electron transfer rate at the interface of a glassy carbon electrode

Redox mediators (RM) are an alternative to improve the performance of microbial electrochemical systems (MES) as they help significantly to develop the indirect electron transfer. However, their use is limited when the redox processes between the RM and the electrode surface are not thoroughly understood. The adsorption, the intermolecular interactions with the electrode, and the effects on charge transfer kinetics are important issues in MES such as microbial sensors, microbial electrosynthesis or microbial fuel cells, but are rarely analyzed. Pyocyanin, considered an RM, may present these features due to its chemical structure. Today, the electrochemical studies indicate that pyocyanin can presents adsorption processes on glassy carbon electrodes. However, the effects of adsorption on electron transfer rate and changes as a function of pyocyanin concentration have not yet been studied. Therefore, this work presents an electrochemical study of pyocyanin to determine the effect of concentration and adsorption on the electron transfer rate at a glassy carbon electrode. Analysis of the electrochemical profiles obtained by cyclic voltamperometry (CV) indicates that there is an effect of concentration (C*) on the heterogeneous electron transfer rate constant (k0) since the criterion ΔEp varies as a function of C*. In addition, the peak proportionality parameter Ipa/Ipc and the voltamperometric function Ip/v½ help deduct the adsorption to the electrode. Experimental data obtained by chronocoulometry (CC) and CV, indicate that k0 = 5.7 × 1011 m/s and Rct = 3.40 × 10−16 Ω under the C* = 0.14 mM condition, while k0 = 1.10 × 103 m/s and Rct = 1.60 × 10−7 Ω under the C* = 0.49 mM condition. The differences in k0 and Rct values at different values of C* are due to an accumulation of pyocyanin on the electrode surface in the inner Helmholtz plane (IHP), preventing the electron transfer of bulk-dissolved pyocyanin molecules present in the outer Helmholtz plane (OHP) region. The varying values of α, indicate that a part of the energy of the redox reaction could be employed for the adsorption processes. As for the interactions at the electrode, the values of the Laviron parameter (ν'gθT) indicate that attraction interactions between the pyocyanin molecules and the electrode dominate, since the values of ν'gθT are higher than 0. The results of this study will provide a comprehensive understanding of the redox cycle of pyocyanin. The information will be useful for the future development of electrochemical-microbial systems since that the interactions mediator-electrode may be an operational variable to facilitate their practical applications in environmental, sensing and electrosynthesis areas.

Shungite (Mineralized Carbon) as a Promising Electrode Material for Electroanalysis.

In this study, two different types of amorphous carbonaceous Precambrian rock, classified as noble elite shungite and black raw shungite, were tested as possible electrode materials of natural origin. Both types were machined into cylindrical shapes to form the corresponding solid electrodes and their physicochemical and electrochemical properties were compared with the standard glassy carbon electrode (GCE). The raw stones were first subjected to microscopic imaging by using scanning electron microscopy and energy-dispersive X-ray spectroscopy, both of which indicated significant differences in their morphology and in the content of impurities. An electrode prototype manufactured from noble elite shungite (EShE) with a carbon content of about 94% (w/w) has offered a very satisfactory electrochemical performance with a nearly identical heterogeneous electron-transfer rate constant of 7.8 × 10-3 cm s-1 for ferro/ferricyanide redox couple, a slightly narrower potential range (~2.1 V) and a relatively low double-layer capacitance (of ca. 50 μF), resulting in low background currents comparable to those at the GCE. In contrast, the second electrode based on black raw shungite (BShE) with a carbon content of ca. 63% (w/w) exhibited markedly worse electrochemical properties and more than four times higher double-layer capacitance, both of which were probably due to the presence of poorly conductive impurities. The whole study has been completed with three different examples of electroanalytical applications, revealing that the first type, EShE, is a more suitable material for the preparation of electrodes and may represent a cheap alternative to commercially marketed products.

Progress toward a better understanding of the urea oxidation by electromediation of Ni(III)/Ni(II) system in alkaline media

Current treatments of wastewater containing urea are energy intensive and release significant quantities of gaseous nitrous oxide. The anodic oxidation of urea by electromediation of Ni(III)/Ni(II) system in alkaline media is a promising alternative: the nitrogenous pollution is decreased while producing hydrogen at the cathode. Firstly, this study aims to deeply investigate the phenomena occurring at the interface, between electrode and electrolyte, in particular by proposing an original methodology enabling to separately study both steps,i.e. the Ni(II) electro-oxidation and the subsequent indirect heterogeneous urea oxidation. Indeed, the variation the potential scan rate, enables (i) to study the effect of the operating parameters (concentration, temperature, angular velocity of a rotating disk electrode) on the rate of each mechanism step, and to (ii) determine key parameters of the overall process (activation energy, diffusion coefficient, anodic charge transfer coefficient and heterogeneous electron transfer rate constant). In a second time, results of urea electrolysis exhibiting high (∼ 80%) urea conversions, carried out at laboratory scale (1.4 g of urea) are discussed. The effect of some operating parameters (alkalinity, temperature, presence of an anionic separator or not) is examined, thanks to a set of analytical methods developed to establish complete mass balances of the products on the liquid phase. Cyanate, ammonium, carbonate and nitrite ions are identified to represent more than 80 % of the destroyed urea. Their respective quantities appear to be dependent of the operating conditions. This study constitutes an essential preliminary step before designing urea electrochemical process operating at larger scale.

Promoting Electron Transfer Kinetics and Adsorption Capacity for the Detection of Furazolidone in Real Food Samples by Using Ag-core@Fe3O4-Shell-Based Electrochemical Sensing Platform

In this study, the preparation of core/shell Ag@Fe3O4 nanoparticles (NPs) and its potential application toward highly sensitive electrochemical detection of furazolidone (FZD) have been reported. UV–visible spectroscopy, X-ray diffraction, scanning electron microscopy, and Zeta sizer are systematically carried out to confirm the formation, size distribution, and composition of Ag@Fe3O4 NPs. By computing the electrochemical characteristic parameters such as electrochemically active surface area (ECSA), electron-transfer resistance (Rct), standard heterogeneous rate constant (k0), adsorption capacity (Γ), and electron transfer rate constant (ks), the Ag@Fe3O4-modified electrode possessed remarkably enhanced electrochemical sensing performance for FZD determination compared to the unmodified screen-printed electrode (SPE). This enhancement of electrochemical activity can be attributed to the fast electron transfer kinetics and great adsorption capacity that arise from the synergistic coupling between the good electrical conductivity of the core AgNPs and the porosity of the protective Fe3O4 shell. Under optimum conditions, the Ag@Fe3O4-based electrochemical nanosensor exhibited not only high sensitivity toward FZD detection of 1.36 μA μM−1 cm−2 in the linear ranges from 0.5–15 μM and 15–100 μM, and low detection limit of 0.24 μM but also long-term stability, repeatability, and anti-interference ability. The applicability of the proposed sensing platform in honey and milk samples was also investigated.

Cyclic voltammetry, square wave voltammetry or electrochemical impedance spectroscopy? Interrogating electrochemical approaches for the determination of electron transfer rates of immobilized redox proteins

In this article, we cross-examine three well-established electrochemical approaches, namely cyclic voltammetry (CV), cyclic square-wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) to dissect the electron transfer (ET) rate of electrostatically immobilized cytochrome c on Ag electrodes. A detailed analysis supported by simulations of redox transition provided three distinct values for the heterogeneous electron transfer (HET) rate constant of cyt c interfaced on COOH-terminated C10-long alkanethiol, i.e., kHET= 47.8 (±2,91) s−1 in CV, kHET= 64.8 (±1,27) s−1 in SWV, and kHET= 26.5 s−1 in EIS. We discuss the obtained discrepancies obtained from electrochemical methods and compare them with the data from spectro-electrochemical experiments. A comprehensive selection list is created from which the most applicable approach can be chosen for studying proteins of interest. CV is most applicable to study the interfaced proteins exhibiting kHET of ca. 0.5 - 70 s−1, SWV is suitable for a broader range of kHET of 5 – 120 s−1 and EIS for kHET of 0.5 to 5 s−1 if alkanethiols are used as immobilization strategy.

A disposable and low-cost laser-scribed graphene electrochemical sensor for simultaneous detection of hydroquinone, paracetamol and methylparaben

• A new disposable LSG sensor was fabricated using Polyetherimide substrate. • Sensor presented high reproducibility, sensitivity, and selectivity. • A LSG sensor was applied to simultaneous detection of emerging pollutants. • A porous graphene-like material with high electrochemical performance was developed. A novel and inexpensive laser-scribed graphene (LSG) sensor using polyetherimide (PEI) substrate was fabricated using CO 2 laser. The material was characterized by scanning electron microscopy (SEM), Raman spectroscopy, and electrochemical techniques, demonstrating a high porous carbonaceous material, which resulted in an electroactive area with 3.4-fold enhancement compared to geometric area and a high heterogeneous electron transfer rate constant (k°) of 3.20x10 -2 cm/s for ferricyanide redox probe. As a proof of applicability, the LSG-PEI sensor was applied for simultaneous detection of hydroquinone (HQ), paracetamol (PA), and methylparaben (MP) emerging pollutants (EP) in tap water and natural (lake) water samples, providing recoveries between 93.1% and 118% with limits of detection of 9.42x10 -8 , 3.23x10 -7 , and 2.95x10 -7 mol/L for HQ, PA, and MP, respectively.

A highly efficient and portable laser-scribed graphene-based electrochemical system for forensic-oriented determination of acepromazine.

Acepromazine (ACP) is a phenothiazine derivative drug commonly used as a tranquilizer veterinary medication due to its sedative properties. Benefiting from sedative properties, ACP has emerged as a drug of abuse and has been associated with drug-facilitated sexual assaults. Herein, we report, for the first time, the electrochemical behavior of ACP using a miniaturized and environmentally friendly laser-scribed graphene-based (LSG) sensor fabricated on a polyetherimide (PEI) substrate. The LSG device presented high porosity, as demonstrated by scanning electron microscopy (SEM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements of the PEI-LSG electrode confirmed the enhanced electroactive area (3.1-fold increase) caused by the rough surface and revealed a low charge transfer resistance of the electrode material, with a heterogeneous electron transfer rate constant (k0) of 8.66 × 10-3 cm s-1 for potassium ferricyanide redox probe. A simple and accurate method was applied to quantify ACP by using square wave voltammetry (SWV) under optimized experimental conditions, which exhibited high sensitivity (0.686 ± 0.008 A L mol-1 cm-2) and a low limit of detection (LOD) of 7.43 × 10-8 mol L-1, with a linear concentration ranging from 0.5 to 100 μmol L-1 ACP. Aiming for on-site analysis, the PEI-LSG sensor was integrated with a miniaturized potentiostat controlled by using a smartphone and applied as proof of applicability to ACP detection in commercial beverage and synthetic urine samples. These studies demonstrated adequate recoveries, ranging from 95.1% to 115.8%. The analytical parameters highlight the robustness and reliability of the proposed method for analyses of ACP directly at a potential crime scene.

An SECM-Based Spot Analysis for Redoxmer-Electrode Kinetics: Identifying Redox Asymmetries on Model Graphitic Carbon Interfaces.

The fundamental process in non-aqueous redox flow battery (NRFB) operation revolves around electron transfer (ET) between a current collector electrode and redox-active organic molecules (redoxmers) in solution. Here, we present an approach utilizing scanning electrochemical microscopy (SECM) to evaluate interfacial ET kinetics between redoxmers and various electrode materials of interest at desired locations. This spot-analysis method relies on the measurement of heterogeneous electron transfer rate constants (kf or kb ) as a function of applied potential (E-E0 '). As demonstrated by COMSOL simulations, this method enables the quantification of Butler-Volmer kinetic parameters, the standard heterogeneous rate constant, k0 , and the transfer coefficient, α. Our method enabled the identification of inherent asymmetries in the ET kinetics arising during the reduction of ferrocene-based redoxmers, compared to their oxidation which displayed faster rate constants. Similar behavior was observed on a wide variety of carbon electrodes such as multi-layer graphene, highly ordered pyrolytic graphite, glassy carbon, and chemical vapor deposition-grown graphite films. However, aqueous systems and Pt do not exhibit such kinetic effects. Our analysis suggests that differential adsorption of the redoxmers is insufficient to account for our observations. Displaying a greater versatility than conventional electroanalytical methods, we demonstrate the operation of our spot analysis at concentrations up to 100 mM of redoxmer over graphite films. Looking forward, our method can be used to assess non-idealities in a variety of redoxmer/electrode/solvent systems with quantitative evaluation of kinetics for applications in redox-flow battery research.

In-Situ Probing the Interface Electrochemical Properties of Chalcopyrite Modified by Amidoxime-Dithiocarbamate Ester: Implications to Flotation Mechanism

ABSTRACT The adsorption of a conductive mineral toward a collector changes its interface electrochemical property, implying the hydrophobization mechanism of froth flotation. Herein, the interface electrical behavior of chalcopyrite was investigated by in situ scanning electrochemical microscopy (SECM). And the results demonstrated that the treatment of N, N-diethyl-S-[2-amino-2-(hydroxyimino) ethyl] dithiocarbamate ester (DEAHEDTC) significantly reduced the tip feedback current i and heterogenous electron transfer rate constant k of chalcopyrite interface, implying the self-assembly of DEAHEDTC on chalcopyrite surface. The adsorption mechanism investigations further revealed that both DEAHEDTC’s C(=NOH)-NH2 and N-C(=S) groups combined with the surface Cu atom(s) of chalcopyrite, leaving its hydrophobic groups outward against chalcopyrite. For the hydrophobic groups that are non-conducting, the electrochemical activity of chalcopyrite interface decreased. While the hydrophobization of DEAHEDTC returned a high flotation recovery of chalcopyrite particles.

Well-Dispersive Polypyrrole and MoSe2 Embedded in Multiwalled Carbon Nanotube@Reduced Graphene Oxide Nanoribbon Electrocatalysts as the Efficient Counter Electrodes in Rigid and Plastic Dye-Sensitized Solar Cells

In this study, a core–shell structured multiwall carbon nanotube@reduced graphene oxide nanoribbon (MWCNT@rGNR) was prepared by the facile unzipping of MWCNTs with mild conditions to synthesize the composites of the MWCNT@rGNR and polypyrrole (PPy) or MoSe2, which were used as the electrocatalysts for the counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). The transmission electron microscopy image of the MWCNT@rGNR showed a graphene sheet structure found on both sides of the MWCNTs, indicating a central core of the MWCNTs and its shell of the rGNR. The obtained MWCNT@rGNR functionalized with PPy or MoSe2 was envisaged to have the advantages of both component, that are the unique electronic structure of the MWCNT@rGNR and the synergistic effects of conductive PPy or electrocatalytically active MoSe2, respectively. The DSSCs with PPy/MWCNT@rGNR0.3 and MoSe2/MWCNT@rGNR0.3 showed comparable efficiency (photoelectric conversion efficiency, PCE = 7.48 and 8.34%, respectively), short-circuit current (Isc = 17.97 and 17.11 mA cm–2, respectively), and open-circuit voltage (Voc = 0.80 and 0.84 V, respectively) without any loss of the fill factor (FF = 0.52 and 0.58, respectively) as compared to the cell fabricated using a standard Pt electrode. The PCE of a standard Pt CE was 7.70% with an Isc of 16.09 mA cm–2, Voc of 0.76 V, and FF of 0.63. According to the results of the electrochemical measurements, composites with PPy or MoSe2 showed better electrocatalytic activity, higher redox-active surface area, and extremely large heterogeneous electron transfer rate constant. The plastic devices assembled with the PPy/MWCNT@rGNR0.3 and MoSe2/MWCNT@rGNR0.3 coated on a flexible plastic substrate (indium tin oxide-coated polyethylene naphthalate; ITO/PEN)exhibited impressive PCEs of 4.61 and 5.25%, respectively, comparable to those coated on the rigid fluorine-doped tin oxide glass substrate. This work presented a facile low-temperature method to fabricate high-performance MWCNT@rGNR composite-based CEs to make them applicable to large-scale plastic DSSCs.