Electrochemistry-mass spectrometry for mechanism study of oxygen reduction at water/oil interface

Electrochemistry methods have been widely employed in the development of renewable energy, and involved in various processes, e.g. water splitting and oxygen reduction. Remarkable progress notwithstanding, there are still many challenges in further optimization of catalysts to achieve high performance. For this purpose, an in-depth understanding of reaction mechanism is needed. In this study, an electrochemistry-mass spectrometry method based on a Y-shaped dual-channel microchip as electrochemical cell and ionization device was demonstrated. Combined solutions of aqueous phase and oil phase were introduced into mass spectrometer directly when electrochemical reactions were happening to study the reduction of oxygen by decamethylferrocene or tetrathiafulvalene under the catalysis of a metal-free porphyrin, tetraphenylporphyrin, at water/1,2-dichloroethane interfaces. Monoprotonated and diprotonated tetraphenylporphyrin were detected by mass spectrometer, confirming the previously proposed mechanism of the oxygen reduction reaction. This work offers a new approach to study electrochemical reactions at liquid-liquid interface.