In Situ Real-Time Quantitative Determination in Electrochemical Nuclear Magnetic Resonance Spectroscopy.

For the purpose of acquiring highly sensitive and differential spectra in in situ electrochemical nuclear magnetic resonance (EC-NMR) spectroscopy, uniform distributions of amplitudes and phases of radio frequency (RF) fields in the sample are needed for consistent flip angles of all nuclei under scrutiny. However, intrinsic electromagnetic incompatibility exists between such requirements with electric properties of the conductive material in an electrolytic cell, including metallic electrodes and ionic electrolytes. This proposed work presents the adverse repercussions of gradually varying electrolyte conductivity, which is strongly associated with the change of ion concentrations in a real-time electrochemical reaction, on spatial distributions of RF field amplitude and phase in the detective zone of an NMR probe coil. To compensate for such a non-linear trend of the spatial dependent distribution, we eliminate different excitation effects of the RF field on the build-in external standard and the electrolyte both situated in nearly the same detection area, as well as promote the greater accuracy of quantitative determination of reactant concentrations. The reliability and effectiveness of the improved in situ EC-qNMR (quantitative NMR) method are confirmed by the real-time monitoring of the electrochemical advanced oxidation process for phenol, in which instant concentrations of reactants and products are detected simultaneously to verify the degradation reaction scheme of phenol.