Raman spectra of natural manganese oxides

Abstract Manganese oxides occur typically as cryptocrystalline and fine‐grained mixtures of different Mn‐phases, carbonates, silicates, and Fe oxides/hydroxides; thus their characterization by standard methods, such as X‐ray diffraction, is extremely challenging. These materials have been widely used in various applications over the millennia, for example, in art works as pigments for pottery, mural paintings, stained glass, and recently, as nanostructured materials with very attractive physicochemical properties. Furthermore, they are important geomaterials that could play a key role in environmental applications, by controlling the partitioning of arsenic and heavy metals between rocks, soils, and aqueous systems. Raman spectroscopy, which is a punctual and nondestructive technique, has been widely used to characterize these materials. However, literature data are often conflicting and contradictory, usually not allowing a proper identification of the Mn species. In this work, we characterize the most common natural manganese oxides by combining X‐ray powder diffraction, Fourier‐transform infrared spectroscopy, and Raman spectroscopy. Our data show that some manganese oxides have characteristic Raman spectra and can be easily recognized by using Raman spectroscopy alone, whereas integration of Raman data with other techniques is mandatory to characterize minerals that have almost identical Raman spectra. With this respect, Raman spectroscopy is the only technique allowing an easy discrimination between hollandite Ba(Mn 4+ 6 ,Mn 3+ 2 )O 16 and cryptomelane K(Mn 4+ 7 ,Mn 3+ )O 16 . The final goal of this work is to provide reference Raman spectra, acquired on previously well‐characterized Mn samples to facilitate the application of Raman spectroscopy in the study of these geomaterials.