Candidate for Catalyst during Water-Oxidation Reaction in the Presence of Manganese Compounds, from Nanosized Particles to Impurities: Sleep with One Eye Open.

Water-oxidation reaction (WOR) catalysts are critical for energy conversion. WOR is a four-electron oxidation and sluggish reaction. WOR needs a high thermodynamic driving force; it is also a kinetically slow reaction. Different compounds have been used for WOR; among these compounds, Mn materials have proven to be interesting because Mn is low-cost and also nontoxic, at least compared to many transition metals. Naturally, it has also been used in the biological water-oxidizing complex (WOC). Indeed, WOR has occurred on a huge scale in natural photosynthesis.For a long time, efforts have been made to design and synthesize various ligands and generate Mn compounds toward WOR catalysts. However, the addition or removal of electrons inside Mn compounds during harsh WOR conditions can lead to the formation or the breakage of bonds and result in the conversion of a precatalyst to a catalyst.Here, our findings on the conversion of Mn compounds to catalysts during WOR are presented. Many Mn compounds have been claimed to be catalysts for WOR in the presence of various chemical oxidants or under electrophotochemical conditions. Currently, the advances in characterization techniques and different spectroscopic methods have enabled a better understanding of catalysts. Different conversions such as that of the Mn complex to Mn oxide and Mn salts to Mn oxide during WOR have been explained. Indeed, the morphology and size of the Mn oxide formed depend on several factors such as the origin compounds, pH, ligands, and conditions. Thus, different Mn compounds show different activities toward WOR. The biomimetic models with Mn-Ca clusters are also decomposed during WOR. On the other hand, stable Mn complexes such as Mn phthalocyanines, which are very stable in the absence of potential, are easily decomposed during WOR. It is noted that for many of these Mn compounds, two steps result in the formation of Mn oxide during WOR: (i) Mn(II) or (III) leaching into the electrolyte and (ii) deposition of the leached Mn ions into the solution.Considering these steps, it can be seen that challenges remain in the area of Mn compounds, given the fact that even in the catalytic cycle at low oxidation numbers no Mn(II) or (III) should be leached to the electrolyte.