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. [1] [2] [3] [4] [5] [6] [7]
When a monochromatic light beam samples the electrode/solution interface, most of the photons are scattered elastically, with the same energy than the incident light. However, a small fraction is scattered inelastically, being the energy of the laser photons shifted up or down. When the scattering is elastic, the phenomenon is denoted as Rayleigh scattering, while when it is inelastic it is called Raman scattering. Raman spectroscopy combined with electrochemical techniques, makes Raman spectroelectrochemistry a powerful technique in the identification, characterization and quantification of molecules.
The main advantage of Raman spectroelectrochemistry is that it is not limited to the selected solvent, and aqueous and organic solutions can be used. However, the main disadvantage is the intrinsic low Raman signal intensity. Different methods as well as new substrates were developed to improve the sensitivity and selectivity of this multirresponse technique. [4]
For researchers, a few experimental considerations related to Raman spectroelectrochemistry include electrode preparation, cell design, laser parameters, electrochemical sequence and data process. [8]
The Raman resonance effect produces an increase in Raman intensity up to 106 times. In this phenomenon, the monochromatic light interaction with the sample produces the transition of the molecules from the fundamental state to an excited electronic state, instead of a virtual state as in normal Raman spectroscopy. This phenomenon of increased intensity could be observed in materials such as carbon nanotubes. [9]
Surface-Enhanced Raman Scattering (SERS) is a technique capable of increasing Raman signal intensity up to 1011 times. This phenomenon is based on the interaction of monochromatic light with materials that exhibit plasmonic properties. The most common metals used in SERS are nanostructured metals with plasmonic band (gold, silver or copper). Nanostructured electrode surfaces can be generated by depositing metallic nanostructures of these materials. A disadvantage of this phenomenon is, sometimes, the lack of reproducibility of the spectra due to the difficulty of obtaining identical nanostructured surfaces in each experiment. [1] [3] [5] [6] [7] [10] [11]
Surface-oxidation enhanced Raman scattering (SOERS) is a process similar to SERS, which allows the Raman signal to be enhanced when a silver electrode is oxidized in a particular electrolyte composition. This process is carried out at sufficiently positive potentials to ensure the oxidation of the electrode surface. There are significant differences with the SERS effect, but it is a phenomenon that also enhances the Raman signal. [1] [5]
In SHINERS, metallic nanoparticles with plasmonic properties are coated with ultra-thin homogeneous silica or alumina layers, forming isolated nanoparticles. The metallic nucleus (Au or Ag) is responsible of the enhancement of the Raman signals of the nearby molecules, while the coating layers eliminate the influence of the metallic nucleus on the Raman and electrochemical signals by preventing the molecules from being directly adsorbed onto them. Silica and alumina coating can improve the chemical and thermal stability of nanoparticles. This fact has great importance in the in-situ study of catalytic reactions. The high sensitivity of the SHINERS surfaces makes these nanostructures a promising tool for the study of liquid-solid interfaces, especially in spectroelectrochemistry. [3] [12] [13] [14]
Tip-enhanced Raman scattering (TERS) is a technique that provides molecular information at nanoscale. In these experiments, metal nanostructures are replaced by a sharp metal tip of nanometric size, concentrating the roughness directly on a small region that improves the spatial resolution of scanning techniques in Raman spectroscopy. [3] [11] [15] [16] [17]
Different configurations can be used to perform Raman-SEC experiments. Raman scattering provides spectra with very weak Raman bands, therefore, a very well aligned optical configuration is required. Laser has to be focused on the electrode surface and an efficient collection of the scattered photons is mandatory. Many of the instruments used for Raman-SEC are based on the combination of a spectrometer, a potentiostat and a confocal microscope, since it is possible to focus and collect the scattered photons in a highly efficient way. [4] [18] Low resolution Raman spectrometers can be also used, providing suitable results. Using this setup, the sampling area is larger and average information about the electrode surface is obtained.
Typical configurations in Raman-SEC:
The experimental setup to perform Raman spectroelectrochemistry consists of a light source, a spectrometer, a potentiostat, a spectroelectrochemical cell, a three-electrode system, radiation beam conducting devices, data collection and analysis devices. Nowadays, there are commercial instruments that integrate all these elements in a single instrument, significantly simplifying the performance of spectroelectrochemical experiments. [5] [19]
In recent years Raman-SEC has become an important tool in the study of electrochemical processes and in the characterization of many molecules, providing specific in situ information about them. Some applications are: [1] [10] [14] [20]
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.
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.
Raman spectroscopy is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman spectroscopy is commonly used in chemistry to provide a structural fingerprint by which molecules can be identified.
In chemistry and physics, Raman scattering or the Raman effect is the inelastic scattering of photons by matter, meaning that there is both an exchange of energy and a change in the light's direction. Typically this effect involves vibrational energy being gained by a molecule as incident photons from a visible laser are shifted to lower energy. This is called normal Stokes-Raman scattering.
Resonance Raman spectroscopy is a variant of Raman spectroscopy in which the incident photon energy is close in energy to an electronic transition of a compound or material under examination. This similarity in energy (resonance) leads to greatly increased intensity of the Raman scattering of certain vibrational modes, compared to ordinary Raman spectroscopy.
Coherent anti-Stokes Raman spectroscopy, also called Coherent anti-Stokes Raman scattering spectroscopy (CARS), is a form of spectroscopy used primarily in chemistry, physics and related fields. It is sensitive to the same vibrational signatures of molecules as seen in Raman spectroscopy, typically the nuclear vibrations of chemical bonds. Unlike Raman spectroscopy, CARS employs multiple photons to address the molecular vibrations, and produces a coherent signal. As a result, CARS is orders of magnitude stronger than spontaneous Raman emission. CARS is a third-order nonlinear optical process involving three laser beams: a pump beam of frequency ωp, a Stokes beam of frequency ωS and a probe beam at frequency ωpr. These beams interact with the sample and generate a coherent optical signal at the anti-Stokes frequency (ωpr+ωp-ωS). The latter is resonantly enhanced when the frequency difference between the pump and the Stokes beams (ωp-ωS) coincides with the frequency of a Raman resonance, which is the basis of the technique's intrinsic vibrational contrast mechanism.
Surface-enhanced Raman spectroscopy or surface-enhanced Raman scattering (SERS) is a surface-sensitive technique that enhances Raman scattering by molecules adsorbed on rough metal surfaces or by nanostructures such as plasmonic-magnetic silica nanotubes. The enhancement factor can be as much as 1010 to 1011, which means the technique may detect single molecules.
A nanoprobe is an optical device developed by tapering an optical fiber to a tip measuring 100 nm = 1000 angstroms wide.
Near-field scanning optical microscopy (NSOM) or scanning near-field optical microscopy (SNOM) is a microscopy technique for nanostructure investigation that breaks the far field resolution limit by exploiting the properties of evanescent waves. In SNOM, the excitation laser light is focused through an aperture with a diameter smaller than the excitation wavelength, resulting in an evanescent field on the far side of the aperture. When the sample is scanned at a small distance below the aperture, the optical resolution of transmitted or reflected light is limited only by the diameter of the aperture. In particular, lateral resolution of 6 nm and vertical resolution of 2–5 nm have been demonstrated.
Spatially offset Raman spectroscopy (SORS) is a variant of Raman spectroscopy that allows highly accurate chemical analysis of objects beneath obscuring surfaces, such as tissue, coatings and bottles. Examples of uses include analysis of: bone beneath skin, tablets inside plastic bottles, explosives inside containers and counterfeit tablets inside blister packs. There have also been advancements in the development of deep non-invasive medical diagnosis using SORS with the hopes of being able to detect breast tumors.
The Raman microscope is a laser-based microscopic device used to perform Raman spectroscopy. The term MOLE is used to refer to the Raman-based microprobe. The technique used is named after C. V. Raman, who discovered the scattering properties in liquids.
Catherine Margaret Shachaf is an Indian cell biologist. She previously held an instructor position at Stanford University School of Medicine, and has made ground-breaking discoveries in cancer research. Shachaf has spoken at scientific conferences and has published more than 17 journal articles. Her leading work was published in Nature (2004), "MYC Inactivation Uncovers Pluripotent Differentiation and Tumor Dormancy in Hepatocellular Cancer." Shachaf is on the Editorial Board of the International Journal of Green Nanotechnology.
The technique of vibrational analysis with scanning probe microscopy allows probing vibrational properties of materials at the submicrometer scale, and even of individual molecules. This is accomplished by integrating scanning probe microscopy (SPM) and vibrational spectroscopy. This combination allows for much higher spatial resolution than can be achieved with conventional Raman/FTIR instrumentation. The technique is also nondestructive, requires non-extensive sample preparation, and provides more contrast such as intensity contrast, polarization contrast and wavelength contrast, as well as providing specific chemical information and topography images simultaneously.
A localized surface plasmon (LSP) is the result of the confinement of a surface plasmon in a nanoparticle of size comparable to or smaller than the wavelength of light used to excite the plasmon. When a small spherical metallic nanoparticle is irradiated by light, the oscillating electric field causes the conduction electrons to oscillate coherently. When the electron cloud is displaced relative to its original position, a restoring force arises from Coulombic attraction between electrons and nuclei. This force causes the electron cloud to oscillate. The oscillation frequency is determined by the density of electrons, the effective electron mass, and the size and shape of the charge distribution. The LSP has two important effects: electric fields near the particle's surface are greatly enhanced and the particle's optical absorption has a maximum at the plasmon resonant frequency. Surface plasmon resonance can also be tuned based on the shape of the nanoparticle. The plasmon frequency can be related to the metal dielectric constant. The enhancement falls off quickly with distance from the surface and, for noble metal nanoparticles, the resonance occurs at visible wavelengths. Localized surface plasmon resonance creates brilliant colors in metal colloidal solutions.
Tip-enhanced Raman spectroscopy (TERS) is a variant of surface-enhanced Raman spectroscopy (SERS) that combines scanning probe microscopy with Raman spectroscopy. High spatial resolution chemical imaging is possible via TERS, with routine demonstrations of nanometer spatial resolution under ambient laboratory conditions, or better at ultralow temperatures and high pressure.
Christa L. Brosseau is a Canadian chemist, currently a Canada Research Chair at Saint Mary's University (Halifax). Brosseau's research focus is on Electrochemical Surface-Enhanced Raman Spectroscopy.
Photopyroelectric As known that Photopyroelectric can be regarded as –Photo +Pyroelectric,which means any optical systems using a pyroelectric detector or imaging system, In addition, pyroelectricity could be depicted as the capability of the components formulating the transient voltage when heated or cooled. Once the temperature on which they depend changes, the position of the atom will change slightly in the crystal structure. This process of change can also be referred to as the polarization of the material. As a result, the voltage across the crystal will be triggered by this change in polarization. To further explain, when the temperature in the engine is kept constant for a period of time, the voltage in the photovoltage will gradually disappear due to the leakage current. In this sense, leakage is mainly caused by several ways, for example, electrons going through the crystal, ions going through the air, or current leaking through a voltmeter connected to the crystal.
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.
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.
Katrin Kneipp is a German physicist.