In situ vibrational spectroscopy can provide molecular level mechanistic insights missing from purely electrochemical measurements. Surface enhanced Raman spectroscopy (SERS) is a particularly promising method and is employed in aqueous and non-aqueous studies of a variety of electrode reactions. Enhancement of the weak Raman signal is achieved by structuring the electrode surface or by use of SERS probes. This review article highlights the recent use of SERS to study several important electrode reactions; oxygen reduction and evolution, carbon monoxide oxidation and carbon dioxide reduction, and the electrocatalytic oxidation of small organic molecules such as formic acid.
Figure 1:A schematic diagram of the study of electrochemical reaction mechanisms using SERS depicting the reactions covered in this review. The SERS substrate electrode must be structured in a manner to provide the SERS enhancement (see Figure 2) and the reactants, intermediates, and products detected must be located in the region in which the enhancement of the Raman signal is strong for effective detection.
The design of a hemofiltration method that minimizes the side effects produced by accumulation of Pt-based drugs such as cisplatin represents an important technology for cancer treatment. This work establishes the foundation for the development of an efficient platform for the electrochemical hemofiltration and simultaneous sensing of anti-tumour drugs, such as cisplatin and carboplatin, from physiological medium. The electrochemical filtration system is based on a gold surface-modified electrode using tris(carboxyethyl)phosphine (TCEP) ligands as scavengers of the Pt-based drugs complexes. The platinum-phosphine interaction is shown to be more time efficient, as compared to naturally occurring formation of a glutathione-platinum adduct and displayed a highly cooperative nature of binding. Altogether, we demonstrate that the presence of ligands capable of binding to Pt results in a differential spectroscopic and electrochemical response, and the potential to absorb and monitor the concentration of Pt salts in complex aqueous media.
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