Influence of heavy metal sorption pathway on the structure of biogenic birnessite: Insight from the band structure and photostability

Birnessite, primarily formed by biooxidation, is a common semiconducting Mn oxide in nature and a major controller of heavy metals cycling processes. In turn, the heavy metal sorption pathway alters its structural chemistry and thus the electronic structure. We synthesize three kinds of birnessite, namely biogenic (bio-birnessite), Cu coprecipitated (co-birnessite) and Cu adsorbed birnessite (ad-birnessite), to investigate the influence of Cu(II) occupancy on the structure, semiconducting property and photostability of birnessite. XRD show co-birnessite holds the same hexagonal symmetry as bio-birnessite, whereas ad-birnessite transforms to triclinic symmetry as reflected by the splitting reflections at 2.44 and 1.42 Å. The adsorption process is accompanied by a more intense releasing of Mn(II) (156.88 μM/L) from a bio-birnessite analog δ-MnO2 in light than in dark (19.55 μM/L), suggesting the photoreductive releasing of Mn(II) promotes structure transformation. Conformably, both the Mn average oxidation state (AOS) (3.32) and mole ratio of Cu/Mn (0.08) in ad-birnessite is lower than those in co-birnessite (AOS: 3.47, Cu/Mn ratio: 0.17). EXAFS demonstrate different Cu complexing features in ad- and co-birnessite that the ratio of Cu incorporated (INC) into vacancies is 1.16 and 0.45 for ad- and co-birnessite, respectively. UV–vis diffuse reflection spectra (DRS) and photoelectron spectrometer (PS) exhibit the band gap (Eg) and valence band (VB) of bio-birnessite are 2.05 and −5.58 eV, while there is 0.1 and 0.05 eV decrease of Eg, and 0.08 and 0.16 eV lowering of VB in co- and ad-birnessite, respectively. The reduced Eg guarantee them to generate photoelectron-hole pairs under mild indoor visible light, and the lower energy level of VB in ad-birnessite makes its VB holes more reactive to accept electrons from electron donors. Further density functional theory (DFT) calculations focus on interpreting the fine structures brought by different Cu sorption pathways on the electronic structure of birnessite. A Mn vacancy in a 2 × 2 × 1 hexagonal birnessite cell significantly reduces Eg from 1.60 to 0.28 eV by hybridizing Mn 3d and O 2p states in VB. The doped Cu reduces Eg mainly through incorporating Cu 3d orbital in VB. The INC Cu in hexagonal birnessite contributes more to reduce Eg (1.60–0.34 eV) than TCS Cu (1.60–1.20 eV), while in triclinic birnessite cell, TCS Cu causes more obvious reduction of Eg (1.68–0.28 eV) than INC Cu (1.68–1.55 eV). Thus, we conclude the vacancy imposes more effect on the electronic structure of hexagonal co-birnessite than doped Cu in TCS or INC sites; and the band structure of co-birnessite is more sensitive to INC Cu, in contrast to TCS Cu affecting more in ad-birnessite. Overall, the crystal structure differs according to Cu fixation pathway, which imposes a comprehensive effect on band structure and photostability contributed by vacancies, Cu occupancy sites and structural symmetry. Cu coprecipitating with birnessite is suggested as a preferred method in practical clean-up of metals such as Cu, due to the higher adsorption capacity for Cu, better stability of TCS Cu and better photostability influenced by Cu.