Weathering of a copper stratiform deposit (schist) at Salobo, Brazil, has produced two distinct Cu-bearing minerals from a biotite parent: vermiculite and a manganese oxide containing as much as 13% and 25% CuO, respectively. Manganiferous products were formed as the result of an interhorizon transfer of solutions through a fissure system. Thus, the structural orientation of the schists was a major factor in controlling the supergene concentration of Cu. The Cu-vermiculite formed by the weathering of Fe-biotite, although the unweathered biotites in the parent rocks were found to contain no copper, suggesting that Cu was supplied by weathering solutions. X-ray powder diffraction (XRD) and cationexchange capacity data for the Cu-vermiculite differ from those of typical Mg-vermiculite and are similar to those of hydroxy- Al-vermiculite. A comparison of the XRD pattern of the Cu-vermiculite with that of a Cu-free vermiculite indicates that Cu atoms are located in interlayer sites. Cu probably occurs in a brucite-like layer. The position and structure of the Cu K-absorption spectrum suggest that the Cu is divalent and exists in 6-fold coordination.

Secondary minerals formed during simulated weathering of nuclear waste glasses have been identified by analytical electron microscopy. A complete description of the reacted glass, from the outermost surface in direct contact with the leachant solution to the reacting front that migrates into the bulk glass, was obtained. Manganese and iron oxyhydroxide phases and saponite were found to have precipitated onto the residual glass surface from the leachant solution. Iron-bearing smectite, serpentine, and manganese and uranium-titanium oxyhydroxides formed in situ in the glass in several distinct bands at different depths beneath the original surface. This sequential development of secondary phases displays a clear trend toward more order and crystallinity in the phases farthest from the reaction front and indicates that complete restructuring of the glass into crystalline phases did not occur at the interface with fresh glass. Additionally, the formation of a discrete uranium-bearing phase, as opposed to uranium uptake by precipitated phases, suggests that stable actinide phase formation rather than ion exchange may be a possible mechanism for retarding radionuclide release to the environment.

The sorption properties of Co, Cu, Ni, and Ca were studied in a mixed mineral suspension of synthetic MnO2 and Wyoming montmorillonite. The distribution of the sorbed cations between the two solid phases was measured by indirect chemical fractionation with acidified NH2OH-HCl and by direct X-ray spectroscopic analysis of mineral particles using electron microscopy. Electron microscope and NH2OH-HCl measurements of the quantity of Co sorbed on MnO2 agreed within 6%. Seventy-seven, 67, and 69% of the total Co, Cu, and Ni sorbed by the mixed mineral suspension was found on the manganese oxide. The opposite distribution was found for sorbed Ca with 28% on the manganese oxide and 72% on the montmorillonite particles. The observed differences in metal sorption by these minerals are related to the cation-sorption mechanisms of manganese oxide and montmorillonite.

Phenol (benzenol) oxidation by three synthetic manganese oxides (buserite, manganite, and feitknechtite) has been studied in aerated, aqueous, acidified suspensions. The rate of reaction was pH dependent. Oxidation was greatly enhanced below pH 4, when diphenoquinone and p-benzoquinone were identified as the first products. Initial reaction rate was correlated with standard reduction potential (E°) of the oxides following the order: feitknechtite > manganite > buserite. A more gradual process of phenol oxidation after the initial reaction was influenced by electrochemical properties of the solution. High soluble manganese activity and increase in pH adversely affected reaction rates. Thus, the reactivity of the oxides was related to their stability and possibly the ability to readsorb Mn(II), following the order: buserite > manganite > feitknechtite. The results indicate that thermodynamic and electrochemical data for oxides and phenols are useful in predicting under which conditions phenols can be oxidized by a given system.

Lithiophorite is a naturally occurring Mn oxide mineral commonly found in soils and sediments. The usual method of synthesizing lithiophorite is via a hydrothermal process in an autoclave at relatively high temperature and pressure. In the present study, an alternative, reflux method, at atmospheric pressure, for synthesis of lithiophorite was developed successfully. The influence of reaction duration, temperature, type of precursor birnessite (H-birnessite, Na-birnessite, aged Na-birnessite), and pH on the formation of lithiophorite were investigated by reflux treatment of lithium-aluminum hydroxide complex ion ()-exchanged birnessite. The results show that the degree of conversion of lithiophorite decreases with decreasing reaction temperature. Lithiophorite can be obtained at pH values from 5.0 to 9.0, but a circumneutral pH is more favorable for formation at atmospheric pressure. Conversion of Na-birnessite (Bir-OH) to lithiophorite is more favored than aged Na-birnessite (Bir-OH-A). Lithiophorite was not obtained by refluxing the ion-exchanged H-birnessite (Bir-H) sample. The rate of conversion of lithiophorite increases with increasing reflux time. Lithiophorite synthesized by a reflux process has pseudo-hexagonal crystals of 0.1–0.5 µm with a chemical composition of Li0.24Al0.46MnO2.67(H2O)1.25. The results have important implications for the origin and underlying mechanism of lithiophorite formation in the environment.

The removal of Co2+, Ni2+, and Pb2+ from aqueous solutions using a modified zeolite was investigated because of the need to eliminate toxic contaminants from wastewaters. In the present study the ways in which equilibrium, thermodynamics, and kinetics parameters affected the removal of heavy metals were evaluated and compared. An Iranian clinoptilolite with a Si/Al ratio of 6.5 was used as an adsorbent. In order to increase the adsorption capacity of the adsorbent, it was converted to a manganese oxide-coated zeolite (MOCZeo) using various Mn solutions. The initial concentration of metals, pH, contact time, and temperature were the variables studied and optimal conditions were established. The maximum amount of Co2+, Ni2+, AND Pb2+ adsorption on MOCZeo was ascertained. A thermodynamics study, using ΔG, ΔH, and ΔS state functions showed that adsorption of Pb2+ was more spontaneous than that of Co2+, Ni2+ ions. The adsorption of these ions on MOCZeo was an endothermic reaction. Investigation of the adsorption models revealed that the adsorption of Pb2+, Co2+, and Ni2+ on MOCZeo followed both the Langmuir and Freundlich models. Kinetics studies showed that the adsorption of Pb2+, Co2+, and Ni2+ on MOCZeo followed the pseudo-second order kinetics model with a high correlation coefficient.

A low-temperature synthesis method for Mn3O4/graphene is described in this research. Adjusting the reaction time and temperature allows control over the phase and morphology of the synthesized manganese oxide, and therefore the microwave absorbing properties. X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and vector network analysis are used to characterize the phase, morphology, and electromagnetic properties. The results reveal that long reaction time can increase the particle size and high temperature can destroy the initial structure of graphene both of which have negative impact on the microwave absorbing properties. The Mn3O4–graphene composite synthesized in 140 °C for 4 h shows a maximum reflection loss (RL) reaching −20 dB at 14.4 GHz with absorber thickness of 2 mm, as well as an effective absorption bandwidth of more than 5 dB corresponding to RL below −10 dB.

A three-dimensional nanostructured graphene oxide–Mn3O4 hybrid was synthesized by a coprecipitation method and used as an anode material of lithium ion batteries, which reached an initial specific capacity of 1400 mA h/g. This method was developed to simplify the process of fabricating uniform composite nanomaterials for abundant applications. In this work, Mn3O4 particles were coordinately distributed on the surface of reduced graphene oxide nanosheets to avoid detrimental stacking of graphene layers by forming 3D nanostructures, as characterized by a scanning electron microscope. As demonstrated by the in situ observation of a scanning probe microscope, severe pulverization of Mn3O4 particles during charge/discharge processing was significantly abstained when graphene layers constrained swelling and shrinkage. The as-prepared graphene–Mn3O4 nanomaterials exhibited a large specific capacity of 949 mA h/g, high-rechargeable efficiency of ∼98%, and exceptional cyclic stability. After 100 constant-current charging/discharging cycles at 100 mA/g, the specific capacity remained at 792 mA h/g with a coulombic efficiency of 98.1%. Furthermore, the coprecipitation method proposed in this work provides a strategy to fabricate other nanostructured composites for different kinds of applications.

Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present “Oxide Wizard.” This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real space.

Rietveld refinement using synchrotron powder X-ray diffraction data revealed that the crystal structure of synthetic Na-birnessite is triclinic (C1), not monoclinic as was previously reported. The Mn–O octahedra have elongated axial bonds, consistent with Jahn–Teller distortion resulting from partial occupancy by Mn3+. Mean Mn–O distances indicate that Mn sites are ∼2/3 Mn4+ and ∼1/3 Mn3+. The interlayer Na cations and H2O molecules occupy a split site that shows evidence of considerable disorder.