Manganese (Mn) pollution poses a serious threat to the health of animals, plants, and humans. The microbial-mediated Mn(II) removal method has received widespread attention because of its rapid growth, high efficiency, and economy. Mn(II)-oxidizing bacteria can oxidize toxic soluble Mn(II) into non-toxic Mn(III/IV) oxides, which can further participate in the transformation of other heavy metals and organic pollutants, playing a crucial role in environmental remediation. This study aims to conduct a bibliometric analysis of research papers on bacterial Mn(II) oxidation using CiteSpace, and to explore the research hotspots and developmental trends within this field between 2008 and 2023. A series of visualized knowledge map analyses were conducted with 469 screened SCI research papers regarding annual publication quantity, author groups and their countries and regions, journal categories, publishing institutions, and keywords. China, the USA, and Japan published the most significant number of research papers on the research of bacterial Mn(II) oxidation. Research hotspots of bacterial Mn(II) oxidation mainly focused on the species and distributions of Mn(II)-oxidizing bacteria, the influencing factors of Mn(II) oxidation, the mechanisms of Mn(II) oxidation, and their applications in environment. This bibliometric analysis provides a comprehensive visualized knowledge map to quickly understand the current advancements, research hotspots, and academic frontiers in bacterial Mn(II) oxidation.

Manganese oxides (MnxOy) are considered a promising cathode material for aqueous zinc-ion batteries (AZIBs) due to their high theoretical specific capacity, various oxidation states and crystal phases, and environmental friendliness. Nevertheless, their practical application is limited by their intrinsic poor conductivity, structural deterioration, and manganese dissolution resulting from Jahn-Teller distortion. To address these problems, doping engineering is thought to be a favorable modification strategy to optimize the structure, chemistry, and composition of the material and boost the electrochemical performance. In this review, the latest progress on doped MnxOy-based cathodes for AZIBs has been systematically summarized. The contents of this review are as follows: (1) the classification of MnxOy-based cathodes; (2) the energy storage mechanisms of MnxOy-based cathodes; (3) the synthesis route and role of doping engineering in MnxOy-based cathodes; and (4) the doped MnxOy-based cathodes for AZIBs. Finally, the development trends of MnxOy-based cathodes and AZIBs are described.

Manganese oxides reduce arsenic (As) toxicity by promoting aqueous-phase As(III) oxidation and immobilization in natural aquatic ecosystems. In anaerobic water-sediment systems, arsenic exists both in a free state in the liquid phase and in an adsorbed state on iron (Fe) minerals. However, the influence of different manganese oxides on the fate of As in this system remains unclear. Therefore, in this study, we constructed an anaerobic microbial As(V) reduction environment and investigated the effects of three different manganese oxides on the fate of both aqueous-phase and goethite-adsorbed As under different pH conditions. The results showed that δ-MnO2 had a superior As(III) oxidation ability in both aqueous and solid phase due not only to the higher SSA, but also to its wrinkled crystalline morphology, less favorable structure for bacterial reduction, structure conducive to ion exchange, and less interference caused by the formation of secondary Fe-minerals compared to α-MnO2 and γ-MnO2. Regarding aqueous-phase As, δ-MnO2, α-MnO2, and γ-MnO2 required an alkaline condition (pH 9) to exhibit their strongest As(III) oxidation and immobilization capability. For goethite-adsorbed As, under microbial-reducing conditions, all manganese oxides had the highest As immobilization effect in neutral pH environments and the strongest As oxidation effect in alkaline environments. This was because at pH 7, Fe(II) and Mn(II) formed hydrated complexes, which was more favorable for As adsorption. At pH 9, the negatively charged state of goethite hindered As adsorption but promoted the adsorption and oxidation of As by the manganese oxides. Our research offers new insights for optimizing As removal from water using various manganese oxides and for controlling the mobilization of As in water-sediment system under different pH conditions.

Manganese (Mn) is a versatile transition element with diverse oxidation states and significant biological importance. Mn-based nanozymes have emerged as promising catalysts in various applications. However, the direct use of manganese oxides as oxidase mimics remains limited and requires further improvement. In this study, we focus on hydroxylated manganese (MnOOH), specifically the layered form β-MnOOH which exhibits unique electronic and structural characteristics. The two-dimensional β-MnOOH nanosheets were synthesized through a hydrothermal approach and showed remarkable oxidase-like activity. These nanosheets effectively converted the oxidase substrate, 3,3\',5,5\'-tetramethylbenzidine (TMB), into its oxidized form by initiating the conversion of dissolved oxygen into ·O2-, 1O2 and ·OH. However, in the presence of L-cysteine (L-Cys), the catalytic activity of β-MnOOH was significantly inhibited, enabling highly sensitive detection of L-Cys. This sensing strategy was successfully applied for smartphone-based L-Cys assay, offering potential utility in the diagnosis of Cys-related diseases. The exploration of layered β-MnOOH nanosheets as highly active oxidase mimics opens up new possibilities for catalytic and biomedical applications.

Carbon nanofibers (CFs) have been widely applied as electrodes for energy storage devices owing to the features of increased contact area between electrodes and electrolyte, and shortened transmission route of electrons. However, the poor electrochemical activity and severe waste of space hinder their further application as supercapacitors electrodes. In this work, MnO2-x nanoflowers restricted and epitaxial growth in/out carbon nanofibers (MnO2/MnO@CF) were prepared as excellent electrode materials for supercapacitors. With the synergistic effect of uniquely designed structure and the introduction of MnO and MnO2 nanoflowers, the prepared interconnected MnO2/MnO@CF electrodes demonstrated satisfactory electrochemical performance. Furthermore, the MnO2/MnO@CF//activated carbon (AC) asymmetric supercapacitor offered an outstanding long-term cycle stability. Besides, kinetic analysis of MnO2/MnO@CF-90 was conducted and the diffusion-dominated storage mechanism was well-revealed. This concept of \"internal and external simultaneous decoration\" with different valence states of manganese oxides was proven to improve the electrochemical performance of carbon nanofibers, which could be generalized to the preparation and performance improvement of other fiber-based electrodes.

Quantifying manganese (Mn) content in solids is critical for understanding its roles in aquatic ecosystems, soils, water treatment plants and distribution systems. No studies have yet used standard Mn oxides to compare the performance of the numerous digestion methods found in the literature. Nine digestion methods (including USEPA 3050B) were compared using four Mn oxides with varying oxidation states. The HCl concentrate (12.4 M) heated to at least at 40 °C provided quantitative digestion of all Mn oxides tested with ≈ 100 % recovery. HCl concentration is important only for MnO2 digestion, while temperature influences both MnO and MnO2 recovery. Complete recovery of various Al, Cu and Fe standard oxides using a 12.4 M HCl digestion at 95 °C. Digestion of environmental samples for Al, Ca, Fe, Mg and Mn content yielded higher metal content using the HCl method (except for Al). HCl 12.4 M digestion provided better performance than other digestion methods found in the scientific literature because of its high reducing capacity. •Most digestion methods found in the literature do not digest all Mn oxidation states.•Hydrochloric acid is shown to be essential to dissolve all oxidation state of Mn oxides.

This study used a simple mechanical ball milling strategy to significantly improve the ability of Mn2O3 to activate peracetic acid (PAA) for sustainable and efficient degradation of organic micropollutant (like bisphenol A, BPA). BPA was successfully removed and detoxified via PAA activation by the bm-Mn2O3 within 30 min under neutral environment, with the BPA degradation kinetic rate improved by 3.4 times. Satisfactory BPA removal efficiency can still be achieved over a wide pH range, in actual water and after reuse of bm-Mn2O3 for four cycles. The change in hydrophilicity of Mn2O3 after ball milling evidently elevated the affinity of Mn2O3 for binding to PAA, while the reduction in particle size exposed more active sites contributing partially to catalytic oxidation. Further analysis revealed that BPA oxidation in the ball mill-treated Mn2O3 (bm-Mn2O3)/PAA process mainly depends on the bm-Mn2O3-PAA complex (i.e., Mn(III)-OO(O)CCH3) mediated non-radical pathway rather than R-O• and Mn(IV). Especially, the existence of the Mn(III)-PAA complex was definitely verified by in situ Raman spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Simultaneously, density functional theory calculations determined that PAA adsorbs readily on manganese sites thereby favoring the formation of Mn(III)-OO(O)CCH3 complexes. This study advances an in-depth understanding of the underlying mechanisms involved in the manganese oxide-catalyzed activation of PAA for superior non-radical oxidation of micropollutants.

Aluminum-containing deposits are pervasive in drinking water distribution systems (DWDSs). However, the mechanisms driving dissolved Al transformation to pipe deposits remain elusive. This study investigated dissolved Al accumulation in DWDSs by batch experiments and long-term pipe experiments using actual finished water. PVC pipe experiments showed that dissolved Al hardly deposited on clean PVC pipe walls at alkaline pH. However, it could be substantially anchored by the pipe surface covered with Mn and Fe deposits formed from Mn(II) oxidation and Fe(III) precipitation. Batch experiments verified that the synthesized Mn and Fe oxides exhibited a strong capacity for dissolved Al uptake at pH 7.7 and 9.0 (dissolved Al was the dominant form). Biofilms on pipe walls also enhanced dissolved Al accumulation. Iron pipe experiments showed that corroded iron pipes with abundant iron corrosion products readily accumulated Al. Compared to chlorination and chloramination, non-disinfected conditions were more favorable for particulate Al deposition on iron pipe surface, probably due to Al immobilization by biofilms. In addition, continuous Al accumulation in iron pipes enhanced Fe release to pipe water. This study highlighted the important role of metal oxides in dissolved Al accumulation in DWDSs with abundant Mn and Fe solids, which provided new insights into deposit formation and control strategies.

δ-MnO2 is a promising cathode material for aqueous aluminium-ion batteries (AAIBs) for its layered crystalline structure with large interlayer spacing. However, the excellent Al ion storage performance of δ-MnO2 cathode remains elusive due to the frustrating structural collapse during the intercalation of high ionic potential Al ion species. Here, it is discovered that introducing heterogeneous metal dopants with high bond dissociation energy when bonded to oxygen can significantly reinforce the structural stability of δ-MnO2 frameworks. This reinforcement translates to stable cycling properties and high specific capacity in AAIBs. Vanadium-doped δ-MnO2 (V-δ-MnO2) can deliver a high specific capacity of 518 mAh g-1 at 200 mA g-1 with remarkable cycling stability for 400 cycles and improved rate capabilities (468, 339, and 285 mAh g-1 at 0.5, 1, and 2 A g-1, respectively), outperforming other doped δ-MnO2 materials and the reported AAIB cathodes. Theoretical and experimental studies indicate that V doping can substantially improve the cohesive energy of δ-MnO2 lattices, enhance their interaction with Al ion species, and increase electrical conductivity, collectively contributing to high ion storage performance. These findings provide inspiration for the development of high-performance cathodes for battery applications.

The increasing intensity of human activities has led to a critical environmental challenge: widespread metal pollution. Manganese (Mn) oxides have emerged as potentially natural scavengers that perform crucial functions in the biogeochemical cycling of metal elements. Prior reviews have focused on the synthesis, characterization, and adsorption kinetics of Mn oxides, along with the transformation pathways of specific layered Mn oxides. This review conducts a meticulous investigation of the molecular-level adsorption and oxidation mechanisms of Mn oxides on hazardous metals, including adsorption patterns, coordination, adsorption sites, and redox processes. We also provide a comprehensive discussion of both internal factors (surface area, crystallinity, octahedral vacancy content in Mn oxides, and reactant concentration) and external factors (pH, presence of doped or pre-adsorbed metal ions) affecting the adsorption/oxidation of metals by Mn oxides. Additionally, we identify existing gaps in understanding these mechanisms and suggest avenues for future research. Our goal is to enhance knowledge of Mn oxides\' regulatory roles in metal element translocation and transformation at the microstructure level, offering a framework for developing effective metal adsorbents and pollution control strategies.