Strong interfacial charge transfer between hausmannite manganese oxide and alumina for efficient photocatalysis

Well crystalline manganese oxide(Mn_(3)O_(4))nanoparticles anchored on gamma alumina(γ-Al_(2)O_(3))have been successfully tailored via a proficient and cost effective chemical process as an efficient material for photo catalysis.XRD indicated the composite formation ofγ-Al_(2)O_(3) and hausmannite structure of Mn_(3)O_(4).SEM and TEM revealed that hetero structure of Mn_(3)O_(4)/γ-Al_(2)O_(3) exhibits an amalgam of aggregated nanoparticles and nanorods.XPS demonstrated the chemical states of binary nanocomposite.The band gap tuning has been performed withγ-Al_(2)O_(3) nanoparticles by assimilating hausmannite Mn_(3)O_(4) particles into flower like microstructure of Al_(2)O_(3).The photoluminescence spectra affirmed the enhancement in charge separation in Mn_(3)O_(4)/γ-Al_(2)O_(3) binary hybrid photocatalyst.The band gap becomes narrow with the increase in concentrations of Mn_(3)O_(4).The narrowing of band gap is concorded with crystalline domains of primary aggregated particles.To elucidate the mechanism of the photocatalytic activity linear sweep voltammetry was performed.The results showed that Mn_(3)O_(4)/γ-Al_(2)O_(3) nanocomposite revealed the enhancement in current density as compared to pureγ-Al_(2)O_(3) which confirmed the electron transfer from Mn_(3)O_(4) toγ-Al_(2)O_(3) through the interfacial potential gradient in conduction bands.The optimum concentration of 6.0%Mn_(3)O_(4)/γ-Al_(2)O_(3) for hybrid structure showed an excellent photocatalytic activity under visible light due to narrow band gap energy.High degree distribution of Mn_(3)O_(4) nano architects overlying onγ-Al_(2)O_(3) induces a significant synergic effect betweenγ-Al_(2)O_(3) and hausmannite phase of manganese oxide(Mn_(3)O_(4)).This strong interfacial contact betweenγ-Al_(2)O_(3) and Mn_(3)O_(4) endures the quick transfer of photo generated charge carriers across interface.

Effects of cobalt doping on the reactivity of hausmannite for As(Ⅲ)oxidation and As(Ⅴ)adsorption

Hausmannite is a common low valence Mn oxide mineral,with a distorted spinel structure,in surficial sediments.Although natural Mn oxides often contain various impurities of transitional metals(TMs),few studies have addressed the effect and related mechanism of TM doping on the reactivity of hausmannite with metal pollutants.Here,the reactivity of cobalt(Co)doped hausmannite with aqueous As(Ⅲ)and As(Ⅴ)was studied.Co doping decreased the point of zero charge of hausmannite and its adsorption capacity for As(Ⅴ).Despite a reduction of the initial As(Ⅲ)oxidation rate,Co-doped hausmannite could effectively oxidize As(Ⅲ)to As(Ⅴ),followed by the adsorption and fixation of a large amount of As(Ⅴ)on the mineral surface.Arsenic K-edge EXAFS analysis of the samples after As(Ⅴ)adsorption and As(Ⅲ)oxidation revealed that only As(Ⅴ)was adsorbed on the mineral surface,with an average As-Mn distance of 3.25–3.30 A,indicating the formation of bidentate binuclear complexes.These results provide new insights into the interaction mechanism between TMs and low valence Mn oxides and their effect on the geochemical behaviors of metal pollutants.

Pathways of birnessite formation in alkali medium

Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) forma- tion stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buser- ite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrys- tallization after dissolution of the intermediates, and the transformations of the minerals de- pended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of mate- rial sciences.