Attenuated total reflection solid-liquid interface

Many important heterogeneous catalytic reactions occur at the interface between a solid catalyst and liquid or liquid-gas reactants. Notwithstanding the importance of solid-catalyzed reactions in the presence of liquid reactants, relatively little attention has been paid to spectroscopic methods that allow researchers to follow the processes occurring at the solid-liquid interface during reaction. This lack can be explained in part by the fact that there are only a few techniques that give access to information about solid-liquid interfaces, the most prominent of them being attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray absorption fine structure (XAFS) spectroscopy. 

Synthetic surfactants and polymers are probably most often used to modify the characteristics of a solid surface, i.e., they function at the solid - liquid interface, such as in the processes of detergency, lubrication, or the formation of adhesive bonds. The performance of modem FT - IR spectrometers is such that many new applications to the characterization of the solid - liquid interface, particularly in kinetics studies, are possible. Reflection - absorption spectroscopy and attenuated total reflectance (ATR) techniques have been applied to "wet" interfaces, even the air - water interface, and have figured prominently in recent studies of "self -assembled" mono - and multilayers. 

In the various sections of this chapter, I will briefly describe the major characteristics of FT-IR, and then relate the importance of these characteristics to physiochemical studies of colloids and interfaces. This book is divided into two major areas studies of "bulk" colloidal aggregates such as micelles, surfactant gels and bilayers and studies of interfacial phenomena such as surfactant and polymer adsorption at the solid-liquid interface. This review will follow the same organization. A separate overview chapter addresses the details of the study of interfaces via the attenuated total reflection (ATR) and grazing angle reflection techniques. 

Presented below is an example of structure development at the solid-liquid interface for the silica/dodecyltrimethylammonium bromide (C12TAB) system, at pH 4.0 and O.IM NaCl as the background electrolyte, obtained by Singh et aL (11). A combination of different techniques such as adsorption, zeta potential, contact angle and FT-IR attenuated total reflection (ATR) measurements, have been used in this study to clearly illustrate the structural transitions, and the structure of self-assembled surfactant films at different adsorbed amounts of the surfactants at the interface. 

Attenuated total reflection (ATR) spectroscopy is one of the most widely used techniques for surface infrared analysis. Although the phenomenon of total internal reflection of light was described by Newton in the early 17th century, it was not until much later that Harrick and, independently, Fahrenfort were to exploit this phenomenon to obtain absorption spectra and develop the ATR technique. When applied to the study of in situ kinetics of adsorption and reaction of species at liquid/ solid interfaces, ATR spectroscopy can yield valuable surface-chemical data. Such studies have been carried out in a variety of research and technological areas, including biomembranes, biofilms, thin film structure and reactivity, and electrochemistry. ... 

It is also common for pol3rmeric compoimds to form surface regions with compositions different from the bulk material, by selective diffusion of components. This process is termed blooming when the surface component is solid, and bleeding if it is liquid. Sulfur and fatty acid blooms can inhibit adhesion in rubber laminates (3). Laser desorption mass spectroscopy has been employed to identify surface species on vulcanized rubber (4). X-ray scattering methods for the study of polymer surfaces and interfaces have been reviewed (5). Other surface analysis techniques commonly used with polymers include attenuated total reflectance (6-8), electron microprobe (9), Auger electron spectroscopy (10), x-ray photoelectron spectroscopy (11), and scanning probe microscopic methods (12). Overviews on polymer surface analysis have been published (13,14). 

IR absorption, emission, and reflection spectra for molecular species either in solid, liquid, or gas phases arise mostly from various changes in energy due to transitions of molecules from one vibrational or rotational energy state to another. The frequency or wavelength of this energy transition is characteristic of the specific chemical bond vibration and/or rotation in the molecule which are determined by the molecular structure, the masses of the atoms, and the associated vibrational energy coupling. Attenuated total reflectance (ATR) and reflection-mode of IR in conjunction with electrochemical methods allow samples to be examined directly in the solid or liquid state without further preparation and are widely used in the characterization of electrode-electrolyte interface properties. Most of ILs are IR-active molecules. Since ILs are stable and chemically inert, the IR characterization can be easily performed on the IL-based system directly. 

Gong D, Subramaniam VP, Highfield JG, Tang Y, Lai Y, Chen Z (2011) In situ mechanistic investigation at the liquid/solid interface by attenuated total reflectance FTIR ethanol photooxidation over pristine and platinized Ti02 (P25). ACS Catal 1(8) 864—871... 

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