Aránzazu Heras

Spectroelectrochemistry at Screen-Printed Electrodes: Determination of Dopamine

A new device to perform spectroelectrochemical measurements in the UV/visible spectral region using screen-printed electrodes has been developed. Neurotransmitter dopamine has been selected as a proof of concept of the capabilities of the new device. The results obtained have allowed us both to study the oxidation mechanism of dopamine and to carry out the spectroelectrochemical detection of this neurotransmitter. Differences in dopamine oxidation mechanism have been observed depending on the initial concentration. Thus, dopamine concentrations lower than 10(-3) M led to a higher generation of dopaminochrome and its derivatives with a band centered at 305 nm, which was the best wavelength to determine dopamine spectrophotometrically at these concentrations. However, if dopamine concentration is higher than 10(-3) M, dopaminoquinone is stable enough to use its maximum of absorbance, 395 nm, to detect this neurotransmitter. Dopamine concentration can also be calculated from the electrochemical data in spectroelectrochemistry, the results being comparable to that obtained from spectroscopic data. Comparison between spectrophotometric and electrochemical determinations demonstrates that the two methods measure this analyte indistinctively, proving that spectroelectrochemistry represents an autovalidated technique. Partial least-squares regression has also been used, obtaining good results in the full dopamine concentration range. Finally, as spectroelectrochemistry is an intrinsically trilinear technique, PARAFAC has been used to study the effect of probable interfering species.

Development of a Novel Bidimensional Spectroelectrochemistry Cell Using Transfer Single-Walled Carbon Nanotubes Films as Optically Transparent Electrodes

A really easy method to transfer commercial single-walled carbon nanotubes (SWCNTs) to different substrates is proposed. In this paper, a homogeneous transference of SWCNTs films to nonconductor and transparent supports, such as polyethylene terephthalate, glass, and quartz, and to conductor supports, such as indium tin oxide, aluminum, highly ordered pyrolytic graphite, and glassy carbon, was achieved using a very fast, reproducible, and clean methodology. In order to test these transferences, SWCNTs films transferred on quartz were used as working optically UV-vis transparent electrodes due to their optimal electrical and optical properties. A new easy-to-use, homemade optical fiber based cell for bidimensional spectroelectrochemistry was developed, offering the possibility to measure in normal and parallel configuration. The cell was tested with ferrocenemethanol, a compound widely used in electrochemistry but scarcely studied by spectroelectrochemistry, covering the UV-vis spectral region.

Spatial scanning spectroelectrochemistry. Study of the electrodeposition of Pd nanoparticles at the liquid/liquid interface

Spatial scanning spectroelectrochemistry is a new analytical technique that provides spectral information at different distances from an electrified liquid/liquid interface where an electrochemical process takes place. As a proof of concept, we have studied two different electrochemical processes at the electrified liquid/liquid interface: (1) Ru(bpy)(3)(2+) transfer through the water/1,2-dichloroethane interface and (2) electrodeposition of Pd nanoparticles at the water/1,2-dichloroethane interface. The instrumental setup developed consists of a movable slit for the light beam to sample at well-defined positions on both sides of the interface, providing important information about the chemical process occurring. If the slit is scanned at different distances from the interface during an electrochemical experiment, a complete picture of the reactions and equilibria in the diffusion layer can be obtained. For example, in the case of the Ru(bpy)(3)(2+), the experiments show clearly how the complex is transferred from one phase to the other. In the case of electrosynthesis of Pd nanoparticles, it is demonstrated that nanoparticles are not only deposited at the interface but diffuse to the aqueous bulk solution. These in situ observations were confirmed by ex situ experiments using transmission electron microscopy.

Simultaneous UV–Visible Absorption and Raman Spectroelectrochemistry

The development of a new device based on the use of UV-vis bare optical fibers in a long optical path length configuration and the measurement of the Raman response in normal arrangement allows us to perform UV-vis and Raman spectroelectrochemistry simultaneously in a single experiment. To the best of our knowledge, this is the first time that a spectroelectrochemistry device is able to record both spectroscopic responses at the same time, which further expands the versatility of spectroelectrochemistry techniques and enables us to obtain much more high-quality information in a single experiment. Three different electrochemical systems, such as ferrocyanide, dopamine, and 3,4-ethylenedioxythiophene, have been studied to validate the cell and to demonstrate the performance of the device. Processes that take place in solution can be properly distinguished from processes that occur on the electrode surface during the electrochemical experiment, providing a whole picture of the reactions taking place at the electrode/solution interface. Therefore, this device allows us to study a larger number of complex electrochemical processes from different points of view taking into account not only the UV-vis spectral changes in the solution adjacent to the electrode but also the Raman signal at any location. Furthermore, complementary information, which could not be unambiguously extracted without considering together the two spectroscopic signals and the electrochemical response, is obtained in a novel way.

Bidimensional chronoabsorptometric study of electropolymerisation of 4,4′-bis(2-methylbutylthio)-2,2′-bithiophene

Abstract Bidimensional chronoabsorptometry is a novel spectroelectrochemical technique that monitors simultaneously three different signals: current and absorbance both normal to the electrode plane and parallel to this plane during a time in which a fixed potential is imposed. This technique is applied in the visible range to the study of the electropolymerisation of 4,4 ′ -bis(2-methylbutylthio)- 2,2 ′ -bithiophene (MBTBT). Experiments are performed in a spectroelectrochemical cell under finite diffusion conditions (thin layer cell) with the aim of interpreting the processes taking place both at the electrode surface and in the adjacent solution during the potentiostatic electrogeneration and deposition of the polymer. Correlations are drawn out among the trends of the oligomers concentration in solution, the polymer electrodeposition and charging, and the current flow, on the time scales of the different steps of the process.

A spectroelectrochemical approach to the electrodeposition of bismuth film electrodes and their use in stripping analysis

UV-vis reflection spectroelectrochemistry has proven to be a very useful multiresponse technique to evaluate the quality of bismuth films obtained by electrochemical deposition on glassy carbon electrodes (GCEs). Bismuth films have recently emerged as a promising and environmental friendly alternative to mercury electrodes for stripping analysis. Spectroelectrochemical measurements, carried out in a flow cell, allowed us to follow in situ the electrodeposition and stripping of bismuth and cadmium. Electrochemical and spectroscopic responses individually have led to successfully quantify the amount of cadmium in test solutions.

Optically transparent electrodes for spectroelectrochemistry fabricated with graphene nanoplatelets and single-walled carbon nanotubes

Optically transparent electrodes (OTEs) are needed for a wide range of applications such as solar cells, printable electronics, touch screens, light emitting diodes or flexible displays. Furthermore, OTEs are required for normal transmission spectroelectrochemistry measurements to obtain simultaneously electrochemical and spectroscopic responses. The search for new materials with a good transparency and conductivity, the basic requirements for an OTE, is outstanding. For this reason, carbon allotropes, such as graphene nanoplatelets (GNPs) and single-walled carbon nanotubes (SWCNTs), have been used in the present work in order to fabricate GNPs/SWCNTs-OTEs. The methodology used to fabricate these hybrid electrodes, based on vacuum filtration techniques, has several advantages such as the use of commercial nanomaterials, an easy cleaning of the final electrode and the availability of the process to almost any laboratory. The optimization of transparency and conductivity of these new electrodes has been achieved by design of experiments, showing that a percolation threshold of SWCNTs needs to be reached to ensure a minimum conductivity. The suitable performance of the GNPs/SWCNTs-OTEs has been validated by studying a film of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by spectroelectrochemistry.

In-situ Evidence of the Redox-State Dependence of Photoluminescence in Graphene Quantum Dots

Changes in the optical properties of graphene quantum dots (GQD) during electrochemical reduction and oxidation were investigated by photoluminescence (PL) spectroelectrochemistry, which provided direct in situ evidence of the dependence of GQD luminescence on their redox state. We demonstrated that GQD PL intensity was enhanced upon reduction (quantum yield increased from 0.44 to 0.55) and substantially bleached during oxidation (quantum yield ∼0.12). Moreover, PL emission blue/red-shifted upon GQD reduction/oxidation, rendering information about electronic transitions involved in the redox processes, namely, the π → π* and the n → π* transitions between energy levels of the aromatic sp2 domains and the functional groups, respectively. PL intensity changes during GQD reduction/oxidation resulted from a variation in structural changes in GQD as a result of charge injection, as corroborated by in situ Raman spectroelectrochemistry.

Direct Determination of Ascorbic Acid in a Grapefruit: Paving the Way for In Vivo Spectroelectrochemistry

The study of real samples is more complicated than the study of other systems. However, the inherent advantages of UV-vis absorption spectroelectrochemistry should overcome some difficulties related to direct measurements in complex matrices. For this reason, a singular spectroelectrochemistry device has been fabricated and validated. The novel cell is based on single-walled carbon nanotubes, which are filtered and subsequently press-transferred on a polyethylene terephthalate support using a stencil with a custom design. With this new methodology, working, counter, and reference electrodes are completely flat on the surface, where two optical fibers are fixed in a long optical path length configuration. To demonstrate the usefulness of this device and the power of spectroelectrochemistry techniques to solve problems of the current world, this device is used to quantitatively detect the concentration of ascorbic acid in a complex matrix such as a fruit, directly, without any previous sample pretreatment. The ease to fabricate the device, the advantages related to its use, and the excellent results obtained not only with univariate but also with multivariate analysis, shed more light on the analysis of samples as they occur in nature. According to the particular features of this cell, to the best of our knowledge this is the first spectroelectrochemical sensor that can be inserted directly in a biological matrix, laying the groundwork to perform in vivo measurements in a near future.

UV/Vis Spectroelectrochemistry as a Tool for Monitoring the Fabrication of Sensors Based on Silver Nanoparticle Modified Electrodes

A new controlled current multipulse methodology has been developed to modify the screen-printed electrode surface with silver nanoparticles (AgNPs). Spectroelectrochemistry has provided not only information about the type of nanoparticles (NPs) deposited on the electrode surface, but also about the electrosynthesis process. Small NPs without plasmon band are initially generated. Next, these nuclei grow to form bigger NPs in the reduction pulses with a characteristic plasmon band centered at 400 nm. Most of the NPs are generated during the first reduction pulses and a linear growth of the absorbance at a lower reaction rate was obtained in the subsequent pulses. Oxidation pulses do not redissolve completely silver NPs but only partially, meaning that very stable NPs are generated. AgNPs-modified electrodes have been successfully used to determine hydrogen peroxide. Spectroelectrochemistry has also yielded very useful information to understand the voltammetric signal obtained during the reduction of H2O2 on silver modified electrodes.