Manganese-Functionalized Bentonite for Efficient Cadmium Ion Removal from Aqueous Systems

Bentonite is widely used as a sorbent due to its high specific surface area and ion-exchange capacity; however, its properties can be significantly influenced by the presence of additional mineral phases and chemical modification. In this study, the influence of manganese oxides and quartz sand on the sorption properties of bentonite from the Stará Kremnička was systematically investigated, with particular attention to surface characterization by X-ray photoelectron spectroscopy (XPS). The materials were also characterized by X-ray diffraction, FTIR spectroscopy, and zeta potential measurements. XPS analysis revealed that manganese in all modified samples was predominantly present in the Mn(IV) oxidation state, with Mn 2p₃/₂ binding energies of 642.5-642.7 eV, corresponding to MnO₂-type phases. Deconvolution of the O 1s spectra confirmed the presence of lattice oxygen, silicate oxygen, and surface hydroxyl groups. The reason for the modification of mainly natural materials with manganese oxides is their higher affinity for the adsorption of heavy metal cations. The maximum adsorption capacity of natural bentonite was 63.29 mg/g. In bentonite samples modified with manganese oxides, the value increased to 103.09 mg/g for BMn, and to 116.28 mg/g for the MMn mixture. The results demonstrate that sorption behavior is governed by a combination of ion exchange on bentonite and interactions with Mn oxide surface phases, providing new insight into the role of Mn(IV) species in surface-controlled metal binding processes. These findings highlight the importance of surface chemical states in designing efficient bentonite-based sorbents.