Spectroelectrochemistry at the liquid|liquid interface: Parallel beam UV–vis absorption

Martínez, Alberto del Monte; Colina, Álvaro; Dryfe, Robert A. W.; Ruiz, Virginia

doi:10.1016/j.electacta.2008.12.028

Cited by 17 publications

(23 citation statements)

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“…This electrochemical process has been taken as a model in different spectroelectrochemical studies with various configurations. [352][353][354] The main reason to take Ru(bpy)3 2+ as reference system is because it exhibits a welldefined ion transfer at the water|1,2-DCE interface 352 and has a large molar absorption coefficient in water ( water =12794 M -1 cm -1 at 453 nm, experimental value estimated in our laboratory, in accordance with the reported values 353 ). The validation of the new device was performed using cell 1, described above in the experimental section.…”

Section: Instrumentationsupporting

confidence: 81%

“…A diagram describing how the distance is calculated is shown inFigure 4.2 Again the decrease of the absorbance in the aqueous phase is concomitant with the increment of absorbance in the organic phase showing the ion transfer of Ru(bpy)3 2+ across the interface due to the difference of potential applied between the two immiscible solutions.The diffusion coefficient of Ru(bpy)3 2+ in the aqueous phase was calculated from the data obtained in an experiment with the slit placed in a fixed position, in such a way that the light beam passes parallel and adjacent to the interface and samples the aqueous phase. Experimental data recorded during the chronoabsorptiometric experiments were fitted to the model described previously by our group354 . A value of 3.29 x 10 -6 cm 2 s -1 was obtained from the electrical charge and a value of 3.65 x 10 -6 cm 2 s -1 was obtained from the absorbance at 453 nm.…”

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New techniques and devices for UV-Vis absorption spectroelectrochemistry

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Hacen constar: Que la presente memoria resume el trabajo titulado "NEW TECHNIQUES AND DEVICES FOR UV-VIS SPECTROELECTROCHEMISTRY" realizado por D. Daniel Izquierdo Bote en el Área de Química Analítica y bajo nuestra dirección para optar al grado de Doctor por la Universidad de Burgos. Manifestamos nuestra conformidad con el contenido de la memoria y autorizamos su presentación para ser defendida como Tesis Doctoral. Burgos, 15 de septiembre de 2015. Fdo: Álvaro Colina Santamaría Fdo: Mª Aránzazu Heras Vidaurre IV V A mis padres VI VII AGRADECIMIENTOS Esta tesis puede verse como un resumen de mis investigaciones en estos últimos años. Sin embargo, no muestra más que una parte de lo vivido durante esta etapa, y este es el momento de dar las gracias a toda la gente que ha estado junto a mí durante todo este tiempo y que ha ayudado de una manera u otra a que esta tesis doctoral sea una realidad, porque sin su ayuda nunca podría haber tenido lugar. Me gustaría agradecer al Prof. Jesús López Palacios, pozo de sabiduría y humildad, y a mis directores de tesis, el Dr. Álvaro Colina y la Dra. Mª Aránzazu Heras, por su inestimable ayuda y por la confianza puesta en mí durante este tiempo. Pero especialmente, por todo lo que me han enseñado y por las experiencias vividas, tanto dentro del laboratorio entre potenciostatos y espectrofotómetros, como fuera de él, entre cañas y risas. Gracias por todo, especialmente por ayudarme a madurar y crecer tanto nivel científico como a nivel personal. No podría haber deseado mejores jefes/compañeros que ellos para compartir estos años. También quiero dar las gracias a mis argentinas, porque sin ellas esta tesis hubiera sido diferente y porque, gracias a sus complejos he aprendido que a veces las cosas son más complejas de lo que parecen. Gracias al lab-192, mi segunda casa durante este tiempo y por supuesto a sus moradores: David, Nola y Jesús a los que no puedo llamar compañeros, sino amigos. Aún recuerdo con cariño aquel día, en el que al fin empezaba la universidad. Quién me iba a decir ese día, en el aula 12 que después de tanto años, ese chico que estaba sentado a mi lado llamado David y una chica de unas filas VIII más allá, Nola, iban a acabar siendo mis compañeros de viaje. Gracias por estar ahí compartiendo innumerables e inolvidables momentos. Y gracias también a Jesús, ese compañero de escritorio con actitud protónica del que todos debiéramos aprender. Un momento importante durante estos años ha sido la hora del café, necesario algunos días para despejar la cabeza, mirar las cosas desde otra perspectiva o desconectar entre risas y bromas. Por todas estas cosas quiero agradecer a los analíticos: Julia, Hugo, Wil, Ana, Bego y Lorena. Gracias también a todos y cada uno de los compañeros del grupo de Análisis Instrumental y de toda el área de Química Analítica, por su ayuda y compañerismo. I would like to thank Prof. Wolfgang Schuhmann for giving me the opportunity of working in his research group in the Ruhr Universität Bochum. Thanks him and the rest of the group for their help...

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Section: Instrumentationsupporting

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New techniques and devices for UV-Vis absorption spectroelectrochemistry

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“…SEC joins the best of electrochemistry and spectroscopy together during an electron‐transfer process. As can be inferred, this multiresponse and “teamwork” technique has been used in a large number of fields, including, for example, electron transfer processes , chemical reaction mechanisms , side reactions , electrocatalysis , corrosion , conducting polymers , solar cells , memory devices , supercapacitors , synthesis and characterization of nanoparticles , carbon nanomaterials , characterization of metal complexes , liquid/liquid interfaces , electrochromic materials or study of compounds of biological interest , among others.…”

Section: Whatmentioning

confidence: 99%

Spectroelectrochemical Sensing: Current Trends and Challenges

et al. 2019

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Spectroelectrochemistry (SEC) has been used for more than 50 years, but this set of techniques has not been widely used for quantitative analysis. For many years, no commercial instruments were available, which made very difficult to spread the use of SEC. Nowadays, only the creativity of the researchers is required to exploit the capabilities of SEC. This review is written with the aim of showing the potential of SEC, mainly for analytical chemistry. Here, we explain what SEC is, how analytical responses can be obtained, why these techniques are useful for sensors, with a brief description of its advantages in use, and, finally, we try to show the challenges that must be addressed in the next years. SEC can resolve interesting analytical problems using the high amount of data provided by this intrinsic trilinear technique. Given the quantitative analysis point of view of this review, the discussion of the SEC techniques is focused on UV/Vis absorption, photoluminescence and Raman SEC.

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“…In practical laboratory experiments, the interface between the two immiscible liquids is usually defined either by liquid density (by layering the lower density liquid over the higher density liquid [9]), by micro-hole interfaces separating the two liquids [10,11], at triple-phase boundary interfaces generated by microdroplets on the electrode surface [12,13], or with the help of a gel [14] or organogel [15,16] stabilizing the liquid/ liquid interface. The organogel/aqueous interface is particularly convenient as it maintains shape without the need for additional substrates or density considerations.…”

Section: Introductionmentioning

confidence: 99%

Biphasic Voltammetry and Spectroelectrochemistry in Polymer of Intrinsic Microporosity—4-(3-Phenylpropyl)-Pyridine Organogel/Aqueous Electrolyte Systems: Reactivity of MnPc Versus MnTPP

et al. 2018

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A hydrophobic polymer of intrinsic microporosity (PIM-EA-TB) is employed to stabilize an organogel/aqueous electrolyte phase boundary based on an organic water-insoluble 4-(3-phenylpropyl)-pyridine phase. The organogel with electrocatalytic metal complexes embedded is immobilized on glassy carbon or on transparent mesoporous tin-doped indium oxide (ITO) electrodes. Liquid/liquid ion transfer voltammetry is investigated for a 4-(3-phenylpropyl)-pyridine organogel/aqueous electrolyte interface for two types of redox systems: tetraphenylporphyrinato-Mn(III/II) (MnTPP) and phthalocyanato-Mn(III/II) (MnPc). Electron transfer is shown to be coupled to reversible liquid/liquid anion transfer processes for PF 6 − , ClO 4 − , SCN − , and NO 3 − , with a change in mechanism for the more hydrophilic anions Cl − , F − , and SO 4 2−. In situ UV-Vis spectroelectrochemistry reveals reversible Mn(III/II) redox processes coupled to ion transfer for MnTPP. But further complexity and a detrimental side reaction are observed for MnPc causing gradual loss of the electrochemical response in the presence of dioxygen.

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Spectroelectrochemistry at the liquid|liquid interface: Parallel beam UV–vis absorption

Cited by 17 publications

References 43 publications

New techniques and devices for UV-Vis absorption spectroelectrochemistry

New techniques and devices for UV-Vis absorption spectroelectrochemistry

Spectroelectrochemical Sensing: Current Trends and Challenges

Biphasic Voltammetry and Spectroelectrochemistry in Polymer of Intrinsic Microporosity—4-(3-Phenylpropyl)-Pyridine Organogel/Aqueous Electrolyte Systems: Reactivity of MnPc Versus MnTPP

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