pH Transitions and electrochemical behavior during the synthesis of iron oxide nanoparticles with gas-diffusion...

Gas diffusion electrocrystallization (GDEx) was explored for the synthesis of iron oxide nanoparticles (IONPs). A gas-diffusion cathode was employed to reduce oxygen, producing hydroxyl ions (OH^-) and oxidants (H₂O₂ and HO₂ ^-), which acted as reactive intermediates for the formation of stable IONPs. The IONPs were mainly composed of pure magnetite. However, their composition strongly depended on the presence of a weak acid, i.e., ammonium chloride (NH₄Cl), and on the applied electrode potential. Pure magnetite was obtained due to the simultaneous action of H₂O₂ and the buffer capacity of the added NH₄Cl. Magnetite and goethite were identified as products under different operating conditions. The presence of NH₄Cl facilitated an acid-base reaction and, in some cases, led to cathodic deprotonation, forming a surplus of hydrogen peroxide, while adding the weak acid promoted gradual changes in the pH by slightly enhancing H₂O₂ production when increasing the applied potential. This also resulted in smaller average crystallite sizes as follows: 20.3 ± 0.6 at -0.350 V, 14.7 ± 2.1 at -0.550 and 12.0 ± 2.0 at -0.750 V. GDEx is also demonstrated to be a green, effective, and efficient cathodic process to recover soluble iron to IONPs, being capable of removing >99% of the iron initially present in the solution.