In-situ MRI velocimetry of the magnetohydrodynamic effect in electrochemical cells.

Electrochemical reactions have become increasingly important in a large number of processes and applications. The use of NMR (Nuclear Magnetic Resonance) techniques to follow in situ electrochemistry processes has been gaining increasing attention from the scientific community because they allow the identification and quantification of the products and reagents, whereas electrochemistry measurements alone are not able to do so. However, when an electrochemical reaction is performed in situ the reaction rate can be increased by action of the Lorentz force, which is equal to the cross product between the current density and the magnetic field applied. This phenomenon is called the magnetohydrodynamic (MHD) effect. Although this process is beneficial because it accelerates the reaction, it needs to be well understood and taken into account during the in situ electrochemical measurements. The MHD effect is based on increased mass transfer, which is shown by in situ MRI velocimetry here. Images had to be acquired in a rapid manner since current was not pulsed. Significant velocities in a plane parallel to the electrodes alongside with complex flow patterns were detected.

Use of the Relaxometry Technique for Quantification of Paramagnetic Ions in Aqueous Solutions and a Comparison with Other Analytical Methods.

We have demonstrated that the relaxometry technique is very efficient to quantify paramagnetic ions during in situ electrolysis measurements. Therefore, the goal of this work was to validate the relaxometry technique in the determination of the concentration of the ions contained in electrolytic solutions, Cu(2+), Ni(2+), Cr(3+), and Mn(2+), and compare it with other analytical methods. Two different NMR spectrometers were used: a commercial spectrometer with a homogeneous magnetic field and a home-built unilateral sensor with an inhomogeneous magnetic field. Without pretreatment, manganese ions do not have absorption bands in the UV-Visible region, but it is possible to quantify them using relaxometry (the limit of quantification is close to 10(-5) mol L(-1)). Therefore, since the technique does not require chemical indicators and is a cheap and robust method, it can be used as a replacement for some conventional quantification techniques. The relaxometry technique could be applied to evaluate the corrosion of metallic surfaces.

In situ study of the magnetoelectrolysis phenomenon during copper electrodeposition using time domain NMR relaxometry.

Although the effect of magnetic field (B) on electrochemical reactions (magnetoelectrolysis phenomenon) has been long known, it has not been considered in electrochemical reactions analyzed in situ by magnetic resonance methods, such as nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and magnetic resonance imaging (MRI), which are intrinsically performed in the presence of B. In this report, the effect of B on the copper electrodeposition reaction, measured by a low-field (0.23 T) NMR spectrometer, was demonstrated. As expected, an enhancement in the reaction rate in comparison to the ex situ electrodeposition reaction was observed. Such enhancement was not dependent on electrodes/magnetic field orientations. Parallel and perpendicular orientations showed similar electrodeposition rates, which is explained by the cyclotron flows generated by distortions in electric and magnetic field lines near the electrode and the electrode edge. Therefore, NMR spectroscopy is not a passive analytical method, as assumed in preceding in situ spectroelectrochemical studies. Although the magnetoelectrolysis phenomenon demonstrated in this report used a paramagnetic ion, it can also be observed for diamagnetic species, since the magnetoelectrolysis phenomenon is independent of the nature of the species. Consequently, similar convection effects may occur in other electrochemical nuclear magnetic resonance (EC-NMR) experiments, such as the electrochemical reaction of organic molecules, as well as in electrocatalysis/fuel cells, lithium-ion batteries, and experiments that use electrochemical electron paramagnetic resonance (EC-EPR) and electrochemical magnetic resonance imaging (EC-MRI).