D. Ibañez

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.

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.

Interfacial doping of carbon nanotubes at the polarisable organic/water interface: a liquid/liquid pseudo-capacitor

The electrochemical reactivity of single-walled carbon nanotube (SWCNT) films, assembled at a polarisable organic/water interface, has been probed using model redox species. Electrons generated by the oxidation of organic 1,1′-dimethylferrocene (DMFc) to DMFc+ can be transferred through the assembled SWCNT layer and reduce aqueous ferricyanide (Fe(CN)63−) to ferrocyanide (Fe(CN)64−), with a doping interaction observed. Several electrochemical techniques, including cyclic voltammetry and electrochemical impedance spectroscopy (EIS), were employed to confirm that the model redox couples dope/charge the SWCNTs. In situ Raman spectro-electrochemistry was also applied to verify the charge transfer processes occurring at the assembled SWCNT films and confirm that the doping effect of the carbon nanotubes is initiated by electrochemical reactions. This doping interaction indicated that the adsorbed SWCNT films can act as a pseudo-capacitor, showing a high area-normalised capacitance. The deeper understanding of the electrochemical properties of SWCNTs, gained from this study, will help determine the performance of this material for practical applications.

Janus Electrochemistry: Asymmetric Functionalization in One Step

Janus structures represent an overwhelming member of materials with adaptable chemical and physical properties. Development of new synthesis routes has allowed the fabrication of Janus architectures with specific characteristics depending on the final applications. In the case of the membranes, the improvement of wet routes has been limited to the capillary effect, in which the solution can gradually penetrate through the membrane, avoiding a double modification different at each face of the membrane. In this work, we propose a new electrochemical methodology to circumvent the capillary limitation and obtain a double electrochemical functionalization in only one step in a controlled way. This innovative methodology has been validated using a tridirectional spectroelectrochemistry setup. Moreover, the information provided by this optical arrangement should be especially useful for the study of the different processes (ion transfer, assisted ion transfer, and electron transfer) that can take place at liquid/liquid interfaces. Janus electrochemistry allows us to modify the two faces of a free-standing single-walled carbon nanotube electrode in a single experiment. As proof of concept, the free-standing films have been functionalized with two different conducting polymers, polyaniline and poly(3-hexylthiophene), in one electrochemical experiment. According to the obtained results, this new electrochemical methodology will open new gates for the design and functionalization of Janus materials.