Search Results (20)

Spinel-structured hausmannite (Mn(II)Mn(III)₂O₄) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO₂ formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment. Full article

The large molybdenum (Mo) isotope fractionation from seawater is caused by the adsorption of Mo on manganese oxides. However, the effects of the manganese oxide mineralogy (crystal structure) and surface Mo coverage on Mo isotope fractionation have not been investigated. In this study, the isotope fractionation of Mo by adsorption on synthetic todorokite, birnessite, and δMnO₂ was investigated under a wide range of surface Mo coverages. The Mo isotope fractionation changed from Δ^98/95Mo = 2.18 ± 0.05‰ to 2.61 ± 0.06‰ for todorokite; from 1.25 ± 0.05‰ to 2.10 ± 0.05‰ for birnessite; and from 2.19 ± 0.07‰ to 2.73 ± 0.08‰ for δMnO₂. The Mo isotope fractionations of the three manganese oxides were negatively correlated with surface coverage normalized to the specific surface area. The independence of the obtained correlation of the manganese oxide species indicates that the Mo isotope fractionation depends on the surface coverage but not on the mineralogy of the manganese oxides. The experimentally observed Mo isotope fractionation (<2.7‰) in manganese oxides generally underestimates the isotope fractionation in natural ferromanganese oxides (~3‰). According to the dependency of the Mo isotope fractionation on the surface coverage, the underestimation relative to previous experimental studies can be attributed to the lower Mo surface coverage of natural ferromanganese oxides. Full article

Rechargeable magnesium batteries are an attractive alternative to lithium batteries because of their higher safety and lower cost, being spinel-type materials promising candidates for their positive electrode. Herein, MgMn₂O₄ with a tetragonal structure is synthesized via a simple, low-cost Pechini methodology and tested in aqueous media. Electrochemical measurements combined with in-situ Raman spectroscopy and other ex-situ physicochemical characterization techniques show that, in aqueous media, the charge/discharge process occurs through the co-intercalation of Mg²⁺ and water molecules. A progressive structure evolution from a well-defined spinel to a birnessite-type arrangement occurs during the first cycles, provoking capacity activation. The concomitant towering morphological change induces poor cycling performance, probably due to partial delamination and loss of electrical contact between the active film and the substrate. Interestingly, both MgMn₂O₄ capacity retention and cyclability can be increased by doping with nickel. This work provides insights into the positive electrode processes in aqueous media, which is vital for understanding the charge storage mechanism and the correlated performance of spinel-type host materials. Full article

A black substance exuding from fractures was observed in 2012 in Ytterby mine, Sweden, and identified in 2017 as birnessite with the composition M_x[Mn(III,IV)]₂O₄∙(H₂O)_n. M is usually calcium and sodium, with x around 0.5. The Ytterby birnessite is unique, with M being calcium, magnesium, and also rare earth elements (REEs) constituting up to 2% of the total metal content. The biogenic origin of the birnessite was established in 2018. Analysis of the microbial processes leading to the birnessite formation and the REE enrichment has continued since then. The process is fast and dynamic, as indicated by the depletion of manganese and of REE and other metals in the fracture water during the passage over the precipitation zone in the mine tunnel. Studies of the exchangeability of metals in the structure are the main objective of the present program. Exposure to solutions of sodium, calcium, lanthanum, and iron led to exchanges and altered distribution of the metals in the birnessite, however, generating phases with almost identical structures after the exchanges, and no new mineral phases were detected. Exchangeability was more efficient for trivalent elements (REE) over divalent (calcium) and monovalent (sodium) elements of a similar size (ionic radii 90–100 pm). Full article

The transformations of physicochemical properties on manganese oxides during peroxymonosulfate (PMS) activation are vital factors to be concerned. In this work, Mn₃O₄ nanospheres homogeneously loaded on nickel foam are prepared, and the catalytic performance for PMS activation is evaluated by degrading a target pollutant, Acid Orange 7, in aqueous solution. The factors including catalyst loading, nickel foam substrate, and degradation conditions have been investigated. Additionally, the transformations of crystal structure, surface chemistry, and morphology on the catalyst have been explored. The results show that sufficient catalyst loading and the support of nickel foam play significant roles in the catalytic reactivity. A phase transition from spinel Mn₃O₄ to layered birnessite, accompanied by a morphological change from nanospheres to laminae, is clarified during the PMS activation. The electrochemical analysis reveals that more favorable electronic transfer and ionic diffusion occur after the phase transition so as to enhance catalytic performance. The generated SO₄^•− and •OH radicals through redox reactions of Mn are demonstrated to account for the pollutant degradation. This work will provide new understandings of PMS activation by manganese oxides with high catalytic activity and reusability. Full article

A very low concentration of manganese (Mn) in water is a critical issue for municipal and industrial water supply systems. Mn removal technology is based on the use of manganese oxides (MnO_x), especially manganese dioxide (MnO₂) polymorphs, under different conditions of pH and ionic strength (water salinity). The statistical significance of the impact of polymorph type (akhtenskite ε-MnO₂, birnessite δ-MnO₂, cryptomelane α-MnO₂ and pyrolusite β-MnO₂), pH (2–9) and ionic strength (1–50 mmol/L) of solution on the adsorption level of Mn was investigated. The analysis of variance and the non-parametric Kruskal–Wallis H test were applied. Before and after Mn adsorption, the tested polymorphs were characterized using X-ray diffraction, scanning electron microscope techniques and gas porosimetry analysis. Here we demonstrated the significant differences in adsorption level between MnO₂ polymorphs’ type and pH; however, the statistical analysis proves that the type of MnO₂ has a four times stronger influence. There was no statistical significance for the ionic strength parameter. We showed that the high adsorption of Mn on the poorly crystalline polymorphs leads to the blockage of micropores in akhtenskite and, contrary, causes the development of the surface structure of birnessite. At the same time, no changes in the surfaces of cryptomelane and pyrolusite, the highly crystalline polymorphs, were found due to the very small loading by the adsorbate. Full article

Groundwater contamination by potentially harmful elements (PHEs) originating from the weathering of granitic and gneissic rock dissolution poses a public health concern worldwide. This study investigated physicochemical variables and PHEs in the groundwater system and mine water of the Adenzai flood plain region, in Pakistan, emphasizing the fate distribution, source provenance, chemical speciation, and health hazard using the human health risk assessment HHRA-model. The average concentrations of the PHEs, viz., Ni, Mn, Cr, Cu, Cd, Pb, Co, Fe, and Zn 0.23, were 0.27, 0.07, 0.30, 0.07, 0.06, 0.08, 0.68, and 0.23 mg/L, respectively. The average values of chemical species in the groundwater system, viz., H⁺, OH⁻, Ni²⁺, Mn²⁺, Mn³⁺, Cr³⁺, Cr⁶⁺, Cu⁺, Cu²⁺, Cd²⁺, Pb²⁺, Pb⁴⁺, Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, and Zn²⁺, were 1.0 × 10⁻⁴ ± 1.0 × 10⁻⁶, 1.0 × 10⁻⁴ ± 9.0 × 10⁻⁷, 2.0 × 10⁻¹ ± 1.0 × 10⁻³, 3.0 × 10⁻¹ ± 1.0 × 10⁻³, 1.0 × 10⁻²² ± 1.0 × 10⁻²³, 4.0 × 10⁻⁶ ± 2.0 × 10⁻⁶, 4.0 × 10⁻¹¹ ± 2.0 × 10⁻¹¹, 9.0 × 10⁻³ ± 1.0 × 10⁻², 2.0 × 10⁻¹ ± 2.0 × 10⁻³, 7.0 × 10⁻² ± 6.0 × 10⁻², 5.0 × 10⁻² ± 5.0 × 10⁻², 2.0 × 10⁻² ± 1.5 × 10⁻², 6.0 × 10⁻² ± 4.0 × 10⁻², 8.0 × 10⁻³¹ ± 6.0 × 10⁻³¹, 3.0 × 10⁻¹ ± 2.0 × 10⁻⁴, 4.0 × 10⁻¹⁰ ± 3.0 × 10⁻¹⁰, and 2.0 × 10⁻¹ ± 1.0 × 10⁻¹. The mineral compositions of PHEs, viz. Ni, were bunsenite, Ni(OH)₂, and trevorite; Mn viz., birnessite, bixbyite, hausmannite, manganite, manganosite, pyrolusite, and todorokite; Cr viz., chromite and eskolaite; Cu viz., CuCr₂O₄, cuprite, delafossite, ferrite-Cu, and tenorite; Cd viz., monteponite; Pb viz, crocoite, litharge, massicot, minium, plattnerite, Co viz., spinel-Co; Fe viz., goethite, hematite, magnetite, wustite, and ferrite-Zn; and Zn viz., zincite, and ZnCr₂O₄ demarcated undersaturation and supersaturation. However, EC, Ca²⁺, K⁺, Na⁺, HCO₃⁻, Cr, Cd, Pb, Co, and Fe had exceeded the WHO guideline. The Nemerow’s pollution index (NPI) showed that EC, Ca²⁺, K⁺, Na⁺, HCO₃⁻, Mn, Cd, Pb, Co, and Fe had worse water quality. Principal component analysis multilinear regression (PCAMLR) and cluster analysis (CA) revealed that 75% of the groundwater contamination originated from geogenic inputs and 18% mixed geogenic-anthropogenic and 7% anthropogenic sources. The HHRA-model suggested potential non-carcinogenic risks, except for Fe, and substantial carcinogenic risks for evaluated PHEs. The women and infants are extremely exposed to PHEs hazards. The non-carcinogenic and carcinogenic risks in children, males, and females had exceeded their desired level. The HHRA values of PHEs exhibited the following increasing pattern: Co > Cu > Mn > Zn > Fe, and Cd > Pb > Ni > Cr. The higher THI values of PHEs in children and adults suggested that the groundwater consumption in the entire region is unfit for drinking, domestic, and agricultural purposes. Thus, all groundwater sources need immediate remedial measures to secure health safety and public health concerns. Full article

K_xMnO₂ materials with birnessite-type structure are synthetized by two different methods which make it possible to obtain manganese oxides with different degrees of crystallinity. The XPS results indicate that the sample obtained at high temperature (KMn8) exhibits a lower oxidation state for manganese ions as well as a denser morphology. Both characteristics could explain the lower capacity value obtained for this electrode. In contrast, the sample obtained at low temperature (KMn4) or by hydrothermal method presents a manganese oxidation state close to 4 and a more porous morphology. Indeed, in this case higher capacity values are obtained. At current density of 30 mA g⁻¹, the KMn8, KMn4, and HKMn samples display a capacity retention of 88, 82, and 68%, respectively. The higher capacity loss obtained for the HKMn compound could be explained considering that the incorporation of Zn²⁺ in the structure gives rise to the stabilization of a ZnMn₂O₄ spinel-type phase. This compound is obtained in the discharge process but remains in the charge stage. Thus, when this spinel-type phase is obtained the capacity loss increases. Moreover, the stabilization of this phase is more favorable at low current rates where 100% of retention for all samples, before 50 cycles, was observed. Full article

Manganese (Mn) is a major element in various aqueous and soil environments that is sometimes highly concentrated in mine water and other mineral processing wastewater. In this study, we investigated Mn removal from alkaline mine water (pH > 9) with an Mn-coated silica sand packed into a pilot-scale column reactor and examined the specific reaction mechanism using X-ray absorption near-edge structure (XANES) analysis and geochemical kinetic modeling. The kinetic effect of dissolved Mn(II) removal by birnessite (δ-Mn(IV)O₂) at pH 6 and 8 was evaluated at different Mn(II)/Mn(IV) molar ratios of 0.1–10. Our results confirmed the positive effect of the presence of δ-MnO₂ on the short-term removal (60 min) of dissolved Mn. XANES analysis results revealed that δ-MnO₂ was more abundant than Mn(III)OOH in the reactor, which may have accumulated during a long-term reaction (4 months) after the reactor was turned on. A gradual decrease in dissolved Mn(II) concentration with depth was observed in the reactor, and comparison with the kinetic modeling result confirmed that δ-MnO₂ interaction was the dominant Mn removal mechanism. Our results show that δ-MnO₂ contents could play a significant role in controlling Mn removability from mine water in the reactor. Full article

Hybrid nanomaterials based on manganese, cobalt, and lanthanum oxides of different morphology and phase compositions were prepared using a facile single-step ultrasonic spray pyrolysis (USP) process and tested as electrocatalysts for oxygen reduction reaction (ORR). The structural and morphological characterizations were completed by XRD and SEM-EDS. Electrochemical performance was characterized by cyclic voltammetry and linear sweep voltammetry in a rotating disk electrode assembly. All synthesized materials were found electrocatalytically active for ORR in alkaline media. Two different manganese oxide states were incorporated into a Co₃O₄ matrix, δ-MnO₂ at 500 and 600 °C and manganese (II,III) oxide-Mn₃O₄ at 800 °C. The difference in crystalline structure revealed flower-like nanosheets for birnessite-MnO₂ and well-defined spherical nanoparticles for material based on Mn₃O₄. Electrochemical responses indicate that the ORR mechanism follows a preceding step of MnO₂ reduction to MnOOH. The calculated number of electrons exchanged for the hybrid materials demonstrate a four-electron oxygen reduction pathway and high electrocatalytic activity towards ORR. The comparison of molar catalytic activities points out the importance of the composition and that the synergy of Co and Mn is superior to Co₃O₄/La₂O₃ and pristine Mn oxide. The results reveal that synthesized hybrid materials are promising electrocatalysts for ORR. Full article

A cost-effective, iron- and manganese-oxide-supported clinoptilolite-based rock was prepared. Based on its nanoporous structure, it worked as a nanoreactor, thereby providing enhanced functionalities. The mono- and bimetallic Fe- and Mn-oxide-supported clinoptilolite was thoroughly characterized with thermoanalytical FT-IR, XRD, SEM, and XPS spectroscopy. All the spectral procedures that were used confirmed the occurrence of a new MnO₂ phase (predominantly birnessite), including mostly amorphous iron oxi(hydr)oxide (FeO(OH)) species on the surface of the above-synthesized adsorbents. The synthesized products validated a considerably higher adsorption capacity toward Pb(II) pollutants compared to the natural clinoptilolite. The following order of a(max) toward Pb(II) was found: MnOx-zeolite (202.1 mg/g) > FeO(OH)-MnOx-zeolite (101.3 mg/g) > FeO(OH)-zeolite (80 mg/g) > natural zeolite (54.9 mg/g). The adsorption equilibrium data were analyzed by the two-parameter empirical isotherm models Langmuir, Freundlich, and BET as well as the three-parameter Redlich–Peterson isotherm. Full article

The heterogeneous oxidation of Cr(III) to Cr(VI), a toxic inorganic anion, by a synthetic birnessite (δ-MnO₂) was investigated in batch reactions using a combination of analytical techniques including UV–Vis spectrophotometry, microwave plasma–atomic emission spectrometry, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR), to evaluate both the solution speciation of Cr(III)/Cr(VI) and the surface of the reacted δ-MnO₂. The formation of dissolved Mn(II) was determined during the batch reactions to evaluate the extent and stoichiometry of the Cr(III) oxidation reaction. A stoichiometric 3:2 Mn(II):Cr(VI) molar relationship was observed in the reaction products. The reductive dissolution of the δ-MnO₂ by Cr(III) resulted in a surface alteration from the conversion of Mn(IV) oxide to reduced Mn(II) and Mn(III) hydroxides. The results of this investigation show that naturally occurring Cr(III) will readily oxidize to Cr(VI) when it comes in contact with MnO_2, forming a highly mobile and toxic groundwater contaminant. Full article

The synthesis methods used to produce todorokite (10 Å manganate, OMS-1) and birnessite (7 Å manganate), which are abundant in marine manganese nodules, have been studied to confirm whether pure mineral phases can be obtained and to compare their physicochemical characteristics. The physicochemical characteristics of todorokite and its precursor Na–birnessite can vary widely based on the precursors used during their synthesis. Birnessite can be synthesized via three mechanisms, i.e., the oxidation of Mn²⁺, a redox reaction between Mn²⁺ and MnO₄⁻, or the reduction of MnO₄⁻. Herein, four precursors are used to synthesize birnessite using different methods before being transformed into todorokite. The characteristics of the birnessite and todorokite synthesized using different methods are investigated via X-ray diffraction (XRD), chemical analysis, Brunauer–Emmett–Teller (BET), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and field emission scanning electron microscopy (SEM). Based on the method used, birnessite and todorokite exhibit distinct physicochemical features, including crystallinity, crystal structure, specific surface area, oxidation state of manganese, thermal stability, and morphology. Thus, the characteristics of birnessite and todorokite are closely correlated, indicating the importance of designing suitable methods to synthesize them for specific applications. Full article

Hierarchical porous birnessite-MnO₂-based nanostructure composite materials were prepared on a nickel foam substrate by a successive ionic layer adsorption and reaction method (SILAR). Following composition with reduced graphene oxide (rGO) and multiwall carbon nanotubes (MWCNTs), the as-obtained MnO₂, MnO₂/rGO and MnO₂/rGO-MWCNT materials exhibited pore size distributions of 2–8 nm, 5–15 nm and 2–75 nm, respectively. For the MnO₂/rGO-MWCNT material in particular, the addition of MWCNT and rGO enhanced the superb distribution of micropores, mesopores and macropores and greatly improved the electrochemical performance. The as-obtained MnO₂/rGO-MWCNT/NF electrode showed a specific capacitance that reached as high as 416 F·g⁻¹ at 1 A·g⁻¹ in 1 M Na₂SO₄ aqueous electrolyte and also an excellent rate capability and high cycling stability, with a capacitance retention of 85.6% after 10,000 cycles. Electrochemical impedance spectroscopy (EIS) analyses showed a low resistance charge transfer resistance for the as-prepared MnO₂/rGO-MWCNT/NF nanostructures. Therefore, MnO₂/rGO-MWCNT/NF composites were successfully synthesized and displayed enhanced electrochemical performance as potential electrode materials for supercapacitors. Full article

Iron and manganese are ubiquitous in the natural environment. Fe^II-Fe^III layered double hydroxide, commonly called green rust (GR), and Mn^III-Mn^IV birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)₂, Fe^II_aq} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O₂. In oxic conditions for an initial Fe^II/OH⁻ ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of Fe^II species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals. Full article