Spectroelectrochemistry

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Spectroscopic and electrochemical techniques that form the spectroelectrochemistry Tipos SEC.png
Spectroscopic and electrochemical techniques that form the spectroelectrochemistry

Spectroelectrochemistry (SEC) is a set of multi-response analytical techniques in which complementary chemical information (electrochemical and spectroscopic) is obtained in a single experiment. Spectroelectrochemistry provides a whole vision of the phenomena that take place in the electrode process. [1] [2] [3] [4] [5] The first spectroelectrochemical experiment was carried out by Theodore Kuwana, PhD, in 1964. [6]

Contents

The main objective of spectroelectrochemical experiments is to obtain simultaneous, time-resolved and in-situ electrochemical and spectroscopic information on reactions taking place on the electrode surface. [1] The base of the technique consist in studying the interaction of a beam of electromagnetic radiation with the compounds involved in these reactions. The changes of the optical and electrical signal allow us to understand the evolution of the electrode process.

The techniques on which the spectroelectrochemistry is based are:

Spectroelectrochemistry provides molecular, thermodynamic and kinetic information of reagents, products and/or intermediates involved in the electron transfer process. [1] [2] [3] [4] [5]

Classification of spectroelectrochemical techniques

There are different spectroelectrochemical techniques based on the combination of spectroscopic and electrochemical techniques. Regarding electrochemistry, the most common techniques used are:

The general classification of the spectroelectrochemical techniques is based on the spectroscopic technique chosen.

Ultraviolet-visible absorption spectroelectrochemistry

Ultraviolet-visible(UV-Vis) absorption spectroelectrochemistry is a technique that studies the absorption of electromagnetic radiation in the UV-Vis regions of the spectrum, providing molecular information related to the electronic levels of molecules. [10] It provides qualitative as well as quantitative information. UV-Vis spectroelectrochemistry helps to characterize compounds and materials, determines concentrations and different parameters such as absorptivity coefficients, diffusion coefficients, formal potentials or electron transfer rates. [11] [12]

Photoluminescence spectroelectrochemistry

Photoluminescence (PL) is a phenomenon related to the ability of some compounds that, after absorbing specific electromagnetic radiation, relax to a lower energy state through emission of photons. This spectroelectrochemical technique is limited to those compounds with fluorescent or luminescent properties. The experiments are strongly interfered by ambient light. [1] This technique provides structural information and quantitative information with great detection limits. [8]

Infrared spectroelectrochemistry

Infrared spectroscopy is based on the fact that molecules absorb electromagnetic radiation at characteristic frequencies related to their vibrational structure. Infrared (IR) spectroelectrochemistry is a technique that allows the characterization of molecules based on the resistance, stiffness and number of bonds present. It also detects the presence of compounds, determines the concentration of species during a reaction, the structure of compounds, the properties of the chemical bonds, etc. [10]

Raman spectroelectrochemistry

Raman spectroelectrochemistry is based on the inelastic scattering or Raman scattering of monochromatic light when it strikes upon a specific molecule, providing information about vibrational energy of that molecule. Raman spectrum provides highly specific information about the structure and composition of the molecules, such as a true fingerprint of them. [1] It has been extensively used to study single wall carbon nanotubes [13] and graphene. [14]

X-ray spectroelectrochemistry

X-ray spectroelectrochemistry is a technique that studies the interaction of high-energy radiation with matter during an electrode process. X-rays can originate absorption, emission or scattering phenomena, allowing to perform both quantitative and qualitative analysis depending on the phenomenon taking place. [8] [9] [10] All these processes involve electronic transitions in the inner layers of the atoms involved. Particularly, it is interesting to study the processes of radiation, absorption and emission that take place during an electron transfer reaction. In these processes, the promotion or relaxation of an electron can occur between an outer shell and an inner shell of the atom.

Nuclear magnetic resonance spectroelectrochemistry

Nuclear magnetic resonance (NMR) is a technique used to obtain physical, chemical, electronic and structural information about molecules due to the chemical shift of the resonance frequencies of nuclear spins in the sample. Its combination with electrochemical techniques can provide detailed and quantitative information about the functional groups, topology, dynamics and the three-dimensional structure of molecules in solution during a charge transfer process. The area under an NMR peak is related to the ratio of the number of turns involved and the peak integrals to determine the composition quantitatively.

Electron paramagnetic resonance spectroelectrochemistry

Electron paramagnetic resonance (EPR) is a technique that allows the detection of free radicals formed in chemical or biological systems. In addition, it studies the symmetry and electronic distribution of paramagnetic ions. This is a highly specific technique because the magnetic parameters are characteristic of each ion or free radical. [15] The physical principles of this technique are analogous to those of NMR, but in the case of EPR, electronic spins are excited instead of nuclear, that is interesting in certain electrode reactions.

Screen-printed electrode with some of the different types of SEC measurements (absorption, emission, Raman scattering). The figure shows a system of three electrodes: the central disc, corresponding to the working electrode; the semicircle with the largest arc, corresponding to the auxiliary or counter electrode; and the semicircle with the smallest arc, the reference electrode. Andrea Santiuste Lydia Garcia Cristina Moreno.png
Screen-printed electrode with some of the different types of SEC measurements (absorption, emission, Raman scattering). The figure shows a system of three electrodes: the central disc, corresponding to the working electrode; the semicircle with the largest arc, corresponding to the auxiliary or counter electrode; and the semicircle with the smallest arc, the reference electrode.

Advantages and applications

The versatility of spectroelectrochemistry is increasing due to the possibility of using several electrochemical techniques in different spectral regions depending on the purpose of the study and the information of interest. [12]

The main advantages of spectroelectrochemical techniques are:

Due to the high versatility of the technique, the field of applications is considerably wide. [1] [2] [3] [4] [5] [16]

Related Research Articles

<span class="mw-page-title-main">Analytical chemistry</span> Study of the separation, identification, and quantification of matter

Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separation isolates analytes. Qualitative analysis identifies analytes, while quantitative analysis determines the numerical amount or concentration.

<span class="mw-page-title-main">Infrared spectroscopy</span> Measurement of infrared radiations interaction with matter

Infrared spectroscopy is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functional groups in solid, liquid, or gaseous forms. It can be used to characterize new materials or identify and verify known and unknown samples. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer which produces an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance on the vertical axis vs. frequency, wavenumber or wavelength on the horizontal axis. Typical units of wavenumber used in IR spectra are reciprocal centimeters, with the symbol cm−1. Units of IR wavelength are commonly given in micrometers, symbol μm, which are related to the wavenumber in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.

<span class="mw-page-title-main">Spectroscopy</span> Study involving matter and electromagnetic radiation

Spectroscopy is the field of study that measures and interprets electromagnetic spectra. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum.

<span class="mw-page-title-main">Surface science</span> Study of physical and chemical phenomena that occur at the interface of two phases

Surface science is the study of physical and chemical phenomena that occur at the interface of two phases, including solid–liquid interfaces, solid–gas interfaces, solid–vacuum interfaces, and liquid–gas interfaces. It includes the fields of surface chemistry and surface physics. Some related practical applications are classed as surface engineering. The science encompasses concepts such as heterogeneous catalysis, semiconductor device fabrication, fuel cells, self-assembled monolayers, and adhesives. Surface science is closely related to interface and colloid science. Interfacial chemistry and physics are common subjects for both. The methods are different. In addition, interface and colloid science studies macroscopic phenomena that occur in heterogeneous systems due to peculiarities of interfaces.

<span class="mw-page-title-main">Raman spectroscopy</span> Spectroscopic technique

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<span class="mw-page-title-main">Ultraviolet–visible spectroscopy</span> Range of spectroscopic analysis

Ultraviolet (UV) spectroscopy or ultraviolet–visible (UV–VIS) spectrophotometry refers to absorption spectroscopy or reflectance spectroscopy in part of the ultraviolet and the full, adjacent visible regions of the electromagnetic spectrum. Being relatively inexpensive and easily implemented, this methodology is widely used in diverse applied and fundamental applications. The only requirement is that the sample absorb in the UV-Vis region, i.e. be a chromophore. Absorption spectroscopy is complementary to fluorescence spectroscopy. Parameters of interest, besides the wavelength of measurement, are absorbance (A) or transmittance (%T) or reflectance (%R), and its change with time.

<span class="mw-page-title-main">Cyclic voltammetry</span> Method of analyzing electrochemical reactions

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<span class="mw-page-title-main">Surface-enhanced Raman spectroscopy</span> Spectroscopic technique

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<span class="mw-page-title-main">Infrared photodissociation spectroscopy</span>

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Ultraviolet-visible (UV-Vis) absorption spectroelectrochemistry (SEC) is a multiresponse technique that analyzes the evolution of the absorption spectra in UV-Vis regions during an electrode process. This technique provides information from an electrochemical and spectroscopic point of view. In this way, it enables a better perception about the chemical system of interest. On one hand, molecular information related to the electronic levels of the molecules is obtained from the evolution of the spectra. On the other hand, kinetic and thermodynamic information of the processes is obtained from the electrochemical signal.

Raman spectroelectrochemistry (Raman-SEC) is a technique that studies the inelastic scattering or Raman scattering of monochromatic light related to chemical compounds involved in an electrode process. This technique provides information about vibrational energy transitions of molecules, using a monochromatic light source, usually from a laser that belongs to the UV, Vis or NIR region. Raman spectroelectrochemistry provides specific information about structural changes, composition and orientation of the molecules on the electrode surface involved in an electrochemical reaction, being the Raman spectra registered a real fingerprint of the compounds.

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