The in situ coupling
between electrochemistry and spectrometric
techniques can help in the identification and quantification of the
compounds produced and consumed during electrochemical reactions.
The combination of electrochemistry with nuclear magnetic resonance
is quite attractive in this respect, but it has some challenges to
be addressed, namely, the reduction in the quality of the NMR signal
when the metallic electrodes are placed close to or in the detection
region. Since NMR is not a passive technique, the convective effect
of the magnetic force (magnetoelectrolysis), which acts by mixing
the solution and increasing the mass transport, has to be considered.
In seeking to solve the aforementioned problems, we developed a system
of miniaturized electrodes inside a 5 mm NMR tube (outer diameter);
the working and counter electrodes were prepared with a mixture of
graphite powder and epoxy resin. To investigate the performance of
the electrodes, the benzoquinone reduction to hydroquinone and the
isopropanol oxidation to acetone were monitored. To monitor the alcohol
oxidation reaction, the composite graphite–epoxy electrode
(CGEE) surface was modified through platinization. The electrode was
efficient for in situ monitoring of the aforementioned reactions,
when positioned 1 mm above the detection region of the NMR spectrometer.
The magnetoelectrolysis effect acts by stirring the solution and increases
the reaction rate of the reduction of benzoquinone, because this reaction
is limited by mass transport, while no effect on the reaction rate
is observed for the isopropanol oxidation reaction.