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. [1] [2] [3] [4] [5] [6] 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. [2] 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.
UV-Vis absorption SEC allows qualitative analysis, through the characterization of the different present compounds, and quantitative analysis, by determining the concentration of the analytes of interest. Furthermore, it helps to determine different electrochemical parameters such as absorptivity coefficients, standard potentials, diffusion coefficients, electronic transfer rate constants, etc. [7] [8] Throughout history, reversible processes have been studied with colored reagents or electrolysis products. [9] Nowadays, it is possible to study all kinds of electrochemical processes in the entire UV-Vis spectral range, [2] even in the near infrared (NIR). [10]
In UV-Vis absorption SEC , depending on the configuration of the light beam respect to the electrode/solution interface, two types of optical arrangements can be distinguished: normal and parallel configuration. [2] [11]
In normal configuration, the light beam samples perpendicularly the electrode surface. Normal configuration provides optical information related to the changes that take place in the solution adjacent to the electrode and on the electrode surface. [11] The optical path length coincides with the diffusion layer thickness, which is usually in the order of micrometers. This arrangement is the most suitable when the compound of interest is deposited or adsorbed on the working electrode, because it provides information about all processes occurring on the electrode surface. [7]
UV-Vis absorption SEC in normal arrangement can be performed using both transmission and reflection phenomena. [11]
In normal transmission, the light beam passes through a optically transparent working electrode, collecting information about the phenomena that take place on the surface of the electrode and on the solution adjacent to it. [11] Electrodes in this configuration must be composed of materials that have great electrical conductivity and adequate optical transparency in the spectral region of interest. [7]
The external reflection mode was proposed to improve the sensitivity and to use non-transparent electrodes. [2]
In normal reflection, the light beam travels in a perpendicular direction to the working electrode surface on which the reflection occurs. The reflected beam is collected to be analyzed in the spectrometer. It is also possible to work with other incidence and collection angles. This configuration is an alternative when the working electrode is non-transparent. [11] In this configuration, the optical path-length in solution is on the order of twice the diffusion layer thickness. It should be noticed that growth of films on the electrode surface could cause optical interference phenomena. As it is based on reflection phenomenon, in many cases reflectance is used as unit of measurement instead of absorbance. [6]
The parallel configuration or long optical path-length arrangement only provides information about the spectral changes that occur in the solution adjacent to the working electrode surface, improving the sensitivity to soluble compounds because the length of the optical pathway can be as longer as the length of the electrode. [2] [11]
The light beam travels parallel to the working electrode surface, sampling the first micrometers of the solution adjacent to the working electrode surface, and collecting the information on the spectrometer. [6] [11]
Usually, aligning light beams has been a difficult task. However, simple alternatives have been developed to perform measurements in parallel configuration. [2] There are several advantages in this configuration respect to the normal one: better sensitivity, lower detection limits; optically transparent electrodes are not required; and the spectral changes are related only to the diffusion layer. [2] [7] [11]
The experimental set-up used to carry out UV-Vis absorption SEC measurements depends on the chosen configuration and the characteristics of the analyte. The experimental set-up is composed of a light source, a spectrometer, a potentiostat/galvanostat, a SEC cell, a three-electrode system, optical elements to conduct the light beam, and a computer for data collection and analysis. [7] Currently, there are commercial devices that integrate all these elements in a single instrument, simplifying significantly the SEC experiments. [12]
UV-Vis absorption SEC is a recent technique that is continuously evolving. However, many advantages have been observed over other techniques. The most outstanding advantages are: [1] [2] [3] [4] [5]
UV-Vis absorption SEC has been used mainly in different research fields such as: [2] [14]
An optical spectrometer is an instrument used to measure properties of light over a specific portion of the electromagnetic spectrum, typically used in spectroscopic analysis to identify materials. The variable measured is most often the irradiance of the light but could also, for instance, be the polarization state. The independent variable is usually the wavelength of the light or a closely derived physical quantity, such as the corresponding wavenumber or the photon energy, in units of measurement such as centimeters, reciprocal centimeters, or electron volts, respectively.
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.
Spectrophotometry is a branch of electromagnetic spectroscopy concerned with the quantitative measurement of the reflection or transmission properties of a material as a function of wavelength. Spectrophotometry uses photometers, known as spectrophotometers, that can measure the intensity of a light beam at different wavelengths. Although spectrophotometry is most commonly applied to ultraviolet, visible, and infrared radiation, modern spectrophotometers can interrogate wide swaths of the electromagnetic spectrum, including x-ray, ultraviolet, visible, infrared, and/or microwave wavelengths.
A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input. The name is from Greek mono- 'single' chroma 'colour' and Latin -ator 'denoting an agent'.
A potentiostat is the electronic hardware required to control a three electrode cell and run most electroanalytical experiments. A Bipotentiostat and polypotentiostat are potentiostats capable of controlling two working electrodes and more than two working electrodes, respectively.
Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram, which plots the current produced by the analyte versus the potential of the working electrode.
In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.
In electrochemistry, electrosynthesis is the synthesis of chemical compounds in an electrochemical cell. Compared to ordinary redox reactions, electrosynthesis sometimes offers improved selectivity and yields. Electrosynthesis is actively studied as a science and also has industrial applications. Electrooxidation has potential for wastewater treatment as well.
An electrochromic device (ECD) controls optical properties such as optical transmission, absorption, reflectance and/or emittance in a continual but reversible manner on application of voltage (electrochromism). This property enables an ECD to be used for applications like smart glass, electrochromic mirrors, and electrochromic display devices.
An ultramicroelectrode (UME) is a working electrode with a low surface area primarily used in voltammetry experiments. The small size of UMEs limits mass transfer, which give them large diffusion layers and small overall currents at typical electrochemical potentials. These features allow UMEs to achieve useful cyclic steady-state conditions at fast scan rates (V/s) with limited current distortion. UMEs were developed independently by Wightman and Fleischmann around 1980. UMEs enable electrochemical measurements in electrolytes with high solution resistance, such as organic solvents. The low current at an UME limits the Ohmic drop, which conventional electrodes do not limit. Furthermore, the low Ohmic drop at UMEs lead to low voltage distortions at the electrode-electrolyte interface, allowing for the use of two electrodes in a voltammetric experiment instead of the conventional three electrodes.
Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectral range. This confers a significant advantage over a dispersive spectrometer, which measures intensity over a narrow range of wavelengths at a time.
Photoelectrochemistry is a subfield of study within physical chemistry concerned with the interaction of light with electrochemical systems. It is an active domain of investigation. One of the pioneers of this field of electrochemistry was the German electrochemist Heinz Gerischer. The interest in this domain is high in the context of development of renewable energy conversion and storage technology.
Scanning electrochemical microscopy (SECM) is a technique within the broader class of scanning probe microscopy (SPM) that is used to measure the local electrochemical behavior of liquid/solid, liquid/gas and liquid/liquid interfaces. Initial characterization of the technique was credited to University of Texas electrochemist, Allen J. Bard, in 1989. Since then, the theoretical underpinnings have matured to allow widespread use of the technique in chemistry, biology and materials science. Spatially resolved electrochemical signals can be acquired by measuring the current at an ultramicroelectrode (UME) tip as a function of precise tip position over a substrate region of interest. Interpretation of the SECM signal is based on the concept of diffusion-limited current. Two-dimensional raster scan information can be compiled to generate images of surface reactivity and chemical kinetics.
The Cary Model 14 UV-VIS Spectrophotometer was a double beam recording spectrophotometer designed to operate over the wide spectral range of ultraviolet, visible and near infrared wavelengths (UV/Vis/NIR). This included wavelengths ranging from 185 nanometers to 870 nanometers.
Single-Entity Electrochemistry (SEE) refers to the electroanalysis of an individual unit of interest. A unique feature of SEE is that it unifies multiple different branches of electrochemistry. Single-Entity Electrochemistry pushes the bounds of the field as it can measure entities on a scale of 100 microns to angstroms. Single-Entity Electrochemistry is important because it gives the ability to view how a single molecule, or cell, or "thing" affects the bulk response, and thus the chemistry that might have gone unknown otherwise. The ability to monitor the movement of one electron or ion from one unit to another is valuable, as many vital reactions and mechanisms undergo this process. Electrochemistry is well suited for this measurement due to its incredible sensitivity. Single-Entity Electrochemistry can be used to investigate nanoparticles, wires, vesicles, nanobubbles, nanotubes, cells, and viruses, and other small molecules and ions. Single-entity electrochemistry has been successfully used to determine the size distribution of particles as well as the number of particles present inside a vesicle or other similar structures
Spectroelectrochemistry (SEC) is a set of multi-response analytical techniques in which complementary chemical information is obtained in a single experiment. Spectroelectrochemistry provides a whole vision of the phenomena that take place in the electrode process. The first spectroelectrochemical experiment was carried out by Theodore Kuwana, PhD, in 1964.
Screen-printed electrodes (SPEs) are electrochemical measurement devices that are manufactured by printing different types of ink on plastic or ceramic substrates, allowing quick in-situ analysis with high reproducibility, sensitivity and accuracy. The composition of the different inks used in the manufacture of the electrode determines its selectivity and sensitivity. This fact allows the analyst to design the most optimal device according to its purpose.
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.
Electrochemical quartz crystal microbalance (EQCM) is the combination of electrochemistry and quartz crystal microbalance, which was generated in the eighties. Typically, an EQCM device contains an electrochemical cells part and a QCM part. Two electrodes on both sides of the quartz crystal serve two purposes. Firstly, an alternating electric field is generated between the two electrodes for making up the oscillator. Secondly, the electrode contacting electrolyte is used as a working electrode (WE), together with a counter electrode (CE) and a reference electrode (RE), in the potentiostatic circuit constituting the electrochemistry cell. Thus, the working electrode of electrochemistry cell is the sensor of QCM.
Theodore Kuwana (1931–2022) was a chemist and academic researcher known as the founding father of the field of spectroelectrochemistry.