Mn Redox Cycling Research Articles

Efficient degradation of Enrofloxacin with novel magnetic MnFe2O4/NiS2 composite as an activator of peroxymonosulfate

The development of highly active and recoverable heterogeneous catalysts for peroxymonosulfate (PMS) activation to remove the persistent presence of antibiotics in aquatic environments, such as Enrofloxacin (ENR), remains a significant challenge. Here, we introduce a pioneering magnetic nanocomposite catalyst, MnFe2O4-NiS2, synthesized via a two-step hydrothermal process, which activates PMS to efficiently degrade ENR. The optimized 0.25MnFe2O4-NiS2/PMS system reached an ENR removal efficiency of 89.9 % within 90 min, outperforming both NiS2/PMS and MnFe2O4/PMS by 5.6 and 2.5 times, respectively. Quenching experiments and electron spin response analysis confirmed SO4•- and •O2– as the primary reactive oxygen species. The enhanced mediated electron transfer capability of the 0.25MnFe2O4-NiS2 nanocomposite improved the redox cycling of Ni (Ⅱ), Mn (Ⅱ) and Fe (Ⅲ) on its surface, as verified by Density Functional Theory calculations. Furthermore, the activation of surface PMS complexes (PMS*) played a crucial role in ENR degradation. The proposed degradation pathways of ENR were confirmed, and toxicity analysis indicated a decrease in intermediate toxicity with the 0.25MnFe2O4-NiS2/PMS system. This study presents an innovative magnetically recoverable, multifunctional catalyst with easy reusability for potential applications in the degradation of organic pollutants.

Simultaneous removal of nitrate, manganese, zinc, and bisphenol a by a biofilm reactor with β-CD modified corn stover biochar and PU sponges: Performance and microbial community response

In the present study, a biofilm reactor with manganese (Mn) redox cycling was established to remove nitrate (NO3−-N), bisphenol A (BPA), zinc (Zn(II)), and Mn(II) using β-cyclodextrin (β-CD) modified corn stover biochar (BC) and polyurethane sponges loaded with Cupriavidus sp. HY129 and Pantoea sp. MFG10. At C/N = 2.0, HRT = 6 h, Mn(II) = 10.0 mg L−1, and BPA and Zn(II) concentrations = 1.0 mg L−1, the removal efficiencies of NO3−-N, Zn(II), BPA, and Mn(II) were 81.5%, 86.5%, 87.9%, and 75.5%, respectively. The outcomes demonstrated the success that the addition of β-CD could accelerate electron transfer activity and the denitrification process. The remediation of BPA and Zn(II) was mainly through the adsorption of bioprecipitation generated by reactor operation. The bioreactor could preserve the stability of the biological community and the expression of pertinent functional genes under the coercion of BPA and Zn(II).

Simultaneous removal of nitrate, manganese, zinc, and bisphenol a by manganese redox cycling system: Performance and mechanism

The manganese(Mn) redox cycling system in this work was created by combining Mn(IV)-reducing bacteria MFG10 with Mn(II)-oxidizing bacteria HY129. The biomanganese oxides (BMO) generated by strain HY129 were transformed by strain MFG10 to Mn(II), finishing the Mn redox cycling, in which nitrate (NO3–-N) was converted to nitrite, which was further reduced to nitrogen gas. The system could achieve 85.7 % and 98.8 % elimination efficiencies of Mn(ⅠⅠ) and NO3–-N, respectively, at Mn(ⅠⅠ) = 20.0 mg/L, C/N = 2.0, pH = 6.5, and NO3–-N = 16.0 mg/L. The removal of bisphenol A (BPA) and zinc (Zn(II)) at 36 h reached 91.7 % and 89.7 % under the optimal condition, respectively. Furthermore, the Mn redox cycling system can reinforce the metabolic activity and electron transfer activity of microorganisms. The findings showed that the adsorption by bioprecipitation throughout the Mn cycling was responsible for the elimination of Zn(II) and BPA.

Efficient degradation of m-cresol by MnO-doped red mud catalyst activating peroxymonosulfate process: Performance and mechanism

M-cresol, one of phenolics, is highly toxic, refractory, and threatens human health and ecological safety. The study on the efficient m-cresol degradation technologies is crucial and helpful to restrain its discharge into water body. A composite of MnO-doped red mud (RM) to activate peroxymonosulfate (PMS) for the m-cresol degradation was fabricated and employed, favorable to the recycling and utilization of RM. Considering the catalytic activity and cost, 0.1 M/RM@G exhibited an excellent degradation capacity attributing to strong Fe3O4 and MnO synergy and was considered as the best catalyst among the investigative catalysts. 100 % of m-cresol and 71.4 % of COD could be degraded within 90 min under 2 g/L catalyst, 10 mM of PMS, 3-8 of initial pH and 50 mg/L m-cresol in the 0.1 M/RM@G/PMS system. The reaction rate constant (0.045 min−1) of 0.1 M/RM@G was much larger than RM@G (0.012 min−1), ARM (0.0048 min−1) and WRM (0.0028 min−1). Main Mn and Fe active components and abundant mesoporous structures on the catalyst surface could efficiently drove electron transfers, and further accelerated the redox cycles of Mn(III)Mn(II) and Fe(III)Fe(II) for activating PMS. 1O2 played a crucial role in degrading m-cresol. Based on the experiment data, the generation mechanism of radicals and the possible pathways of m-cresol degradation were proposed in the 0.1 M/RM@G/PMS system. This finding provides a new way for the synthesis of the efficient catalyst with RM and optimal operating strategies for the treatment of m-cresol wastewater.

Efficient catalytic ozonation for hexazinone degradation by Fe/Ce-doped MOF derivatives

High catalytic efficiency and strong anti-interference catalyst for refractory pollutants removal remains a challenge for the catalytic ozonation. Metal-organic framework (MOF) have shown excellent performance in catalysis filed, but there is a risk of metal ion leaching. Designing MOF derivatives by high temperature modulation is considered to be an effective way to enhance the performance and reduce leaching risk of MOFs. In this paper, Fe/Ce bimetallic metal–organic framework (FeCe-MOF) was synthesized and three MOF derivatives were prepared by calcination at different temperatures. The performance of MOF derivatives in the degradation of hexazinone via catalytic ozonation and the effects were investigated. The mechanism of catalytic ozonation by FeCe@C-600 was also elucidated by the analysis of structural characterization of the fresh and used FeCe@C-600, electron paramagnetic resonance (EPR) and quenching experiment. FeCe@C-600/O3 system achieved 78.78 % removal of hexazinone and 42.37 % degradation of TOC within 20 min. During the catalytic ozonation, FeCe@C-600 has high structural stability and avoiding the release of metal ions. FeCe@C-600 showed excellent performance to degrade and mineralize of hexazinone, and it is more stable and has wider pH applicability. The electron transfer and redox cycling of Mn+/Mn+1 were promoted along with the conversion of lattice oxygen to oxygen vacancies. The degradation of hexazinone was mainly attributed to the generation of reactive oxygen species (•OH, •O2–, 1O2) during catalytic ozonation. MOF derivatives exhibited good adsorption capacity during the degradation of hexazinone. FeCe@C-600 effectively reduces metal leaching while retaining high catalytic activity, providing new ideas for the development of new efficient and environmentally friendly ozone catalysts.

Efficient removal of tetracycline using magnetic MnFe2O4/MoS2 nanocomposite activated peroxymonosulfate: Mechanistic insights and performance evaluation

In this study, MnFe2O4/MoS2nanocomposite was prepared for activation of peroxymonosulfate (PMS) to remove tetracycline (TC) in aqueous solutions. The results showed that the highest activation efficiency was obtained when the molar ratio of MnFe2O4 to MoS2 was 1:3 (MnFe2O4/MoS2-3). TC removal efficiency in the MnFe2O4/MoS2-3 (MM3)/PMS system reached 92.9 % in 30 min. Radical identification experiments confirmed that SO4•−, •OH and 1O2 were the main reactive oxygen species in the MM3/PMS system. The excellent electron transfer capability of MM3 nanocomposite ensured rapid redox cycling of Mn(II)/Fe(II) on the material surface, thus greatly facilitating the production of reactive oxygen species and the degradation of TC. In addition, over 80 % of TC in natural water backgrounds were degraded by the MM3/PMS system. The MM3 maintained its high activity during repeated five cycles. Thus, the synthesized MnFe2O4/MoS2 nanocomposite is an ideal PMS activator and can be used to the treatment of refractory pollutants.

Fe, Mn-Prussian blue analogue@MXene composites for efficient photocatalytic peroxydisulfate-activated degradation of tetracycline hydrochloride and photoelectrochemical desalination

The utilization of wastewater or saline as a source of clean and safe freshwater is a potential solution to address water pollution and scarcity. In this study, we synthesized a composite material, i. e. Fe, Mn-Prussian blue analogue@MXene, which is highly responsive to visible light and serves as an innovative activator for peroxydisulfate (PDS) in the degradation of tetracycline hydrochloride (TCH). The FeMn-PBA@MXene-0.30 composite, with its unique metal-organic framework (MOF) structure, exhibited excellent photocatalytic activity in the degradation of TCH by activating PDS through dual redox cycles of Mn(II)–C≡N–Fe(III) and Mn(III)–C≡N–Fe(II). A remarkable 93.41% removal of TCH can be achieved at a concentration of 30 mg·L−1 within 120 min. The presence of MXene in the composite may facilitate the efficient electron transportation owing to its excellent conductivity. The influences of various reaction conditions are also investigated, such as the concentration of potassium persulfate (KPS), TCH concentration, and solution pH value. Electron spin resonance (ESR) analysis and trapping experiments revealed the presence of reactive species, including 1O2, ∙OH, and h+, in the FeMn-PBA@MXene-0.30/visible light/PDS system. Furthermore, we demonstrated the application of the FeMn-PBA@MXene-0.30 composite as the photoanode of a solar-assisted photoelectrochemical desalination (SA-PED) device, which combines the TCH degradation with photoelectrochemical desalination. This novel approach enabled simultaneous degradation and desalination, resulting in a significant reduction of 4000-ppm brine to 240 ppm (lower than the freshwater threshold of 500 ppm), with a salt removal efficiency (SRE) of 94.00%. Meanwhile, the degradation rate of TCH (900 mg·L−1) reached up to 98.91% under visible light irradiation. This work not only provides valuable insights into the development of PDS-activated catalysts but also explores new avenues for the multifunctional application of photocatalysts in addressing water pollution and scarcity.

Mn-modified biochars for efficient adsorption and degradation of cephalexin: Insight into the enhanced redox reactivity.

Mn-modified biochars (BCs) were developed by pre-treatment of feedstock (MBCs) or post-modification of biochar (BCM), for simultaneous adsorption and degradation of a model pollutant, cephalexin. The apparent removal rates of cephalexin in the presence of MBCs (2.49 - 6.39×10-2 h-1) and BCM (13.3×10-3 h-1) were significantly higher than that in the presence of biochar prepared under similar conditions (4.2×10-3 h-1). While the •OH generated from the activation of dissolved O2 by the persistent free radicals (PFRs) and phenolic -OH on BC could cause degradation of cephalexin, its removal was drastically enhanced through direct oxidation by the MnOx and related Mn species on Mn-modified BCs. The removal of cephalexin by MBCs decreased as the solution pH was raised from 5.0 to 9.0, which supports the critical role played by Mn3O4 in its oxidation. Removal of cephalexin in the presence of MBCs and Mn3O4 was enhanced with the introduction of Mn(II) ions, suggesting that the Mn3O4 present on MBCs facilitates the re-oxidation of Mn(II) to highly reactive Mn(III). While MnO2 anchored on BCM also enhanced the cephalexin oxidation, the active sites of BC and MnO2 were partially destroyed during post-modification of BC, compromising the redox cycling of Mn(II)/Mn(III) and the generation of •OH. As a result, the performance of BCM in oxidizing cephalexin was inferior to that of MBCs. These findings shed new light on the development of environmentally benign sorbents capable of simultaneously adsorbing and oxidizing organic pollutants.

Mineralogy of the 1.45 Ga Wafangzi manganese deposit in North China: Implications for pulsed Mesoproterozoic oxygenation events

Abstract Ancient manganese (Mn) deposits are primarily characterized by the presence of Mn(II) carbonates that likely formed by the diagenetic reduction of precursor Mn(IV) oxides. As such, Precambrian sedimentary Mn deposits have been used as a line of evidence for the evolution of oxygen in Earth’s surface environments. However, recent studies have shown that these Mn(II)-carbonates have the ability to directly accumulate within anoxic water columns, where free oxygen does not play a role in their formation. This alternative pathway casts uncertainty on the robustness of using ancient Mn deposits to constrain the redox fabric of the past marine water columns. Here, we investigate the Wafangzi Mn and Fe ore deposit from the 1.45 billion-year-old Tieling Formation, North China. The deposit contains Mn(II, III) mineral phases (hausmannite, braunite) as inclusions, or unreacted residues, trapped within Mn(II) carbonate (Ca-rhodochrosite). Some nodules and oolites of Mn(II) and Fe(II)-carbonate phases are also present and display a banded structure with concentric rings. Mn(III) oxide (manganite) is present in a paragenetic assemblage along with hematite and replacement textures with braunite. The negative carbon isotope composition (δ13C, –7‰ to –4‰) from Mn(II) carbonate samples in the Wafangzi Mn deposit which are distinct from that of contemporaneous seawater (~0‰), along with petrographic and speciation analyses, collectively suggest that the Mn(II, III)- and Fe(II)-bearing mineral phases formed through the diagenetic reduction of primary Mn(IV)/Fe(III) minerals coupled to the oxidation of organic matter. Therefore, the Wafangzi Mn deposit suggests the presence of sufficiently oxygenated marine waters, overlying anoxic ferruginous deeper waters with a transitional manganous water layer that could have driven the redox cycling of Mn, Fe, and C. Given the contemporaneous economic Mn deposits in the 1.45 Ga Ullawarra Formation in Western Australia, our findings imply the existence of a transient, and perhaps widespread, pulsed oxygenation event in the mid-Proterozoic oceans.

Co-existing two distinct formation mechanisms of micro-scale ooid-like manganese carbonates hosted in Cryogenian organic-rich black shales in South China

Manganese-rich deposits in the lower member of the Datangpo Formation (DTP) (ca. 663–654 Ma) in South China formed in the aftermath of the Cryogenian Sturtian glaciation. The Mn in the DTP occurs dominantly as rhodochrosite and Ca-rhodochrosite. A hydrothermal origin of the Mn2+ is shown by the rare earth element distribution and significantly high Mn/Fe ratios (3–19, average = 10.1). Previous studies suggested a microbially-mediated process for controlling the DTP black-shale hosted Mn carbonate deposits. However, detailed reports on the formation mechanisms of micro-scale (<2–5 μm) ooid-like Mn carbonates in the DTP have rarely been published. Systematic petrography and geochemical analyses in this study demonstrate the coexistence of two types of micro-scale ooidal-like Mn carbonates formed through two distinct mechanisms, either dominated by microbially-mediated or physiochemically-forced pathways. The Type I Mn carbonate has relatively larger grain size of 2–5 μm and exhibits a radial-concentric microfabric that shows signs of growth banding in the form of alternating light and dark laminae, which mainly express variation in Ca and Mn concentrations. The initial precipitation phase of the Type I Mn carbonate is interpreted to be Mn oxide/hydroxide, based on positive Ce anomalies and selective enrichments of particular trace elements. Novel evidence indicates that the capture of Mn as a carbonate phase directly from the water column by primarily precipitated calcite, which is referred to as the Type II Mn carbonate, has also contributed to the DTP Mn-rich deposits. Multiple roles of organic matter in Mn carbonate formation have been established: (1) catalysed Mn-redox cycling; (2) trapping and transportation of initial mineral precipitates to sediments; (3) serving as a carbon source; (4) regulating the morphology of the Mn carbonate. As a key link for understanding Cryogenian carbon and Mn cycling, specific formation pathways for the DTP Mn-carbonates are likely to have been controlled by given atmospheric-oceanic compositions (including oxygen level, pCO2, and redox conditions) in response to major geological and biological events during the interglacial period. In turn, massive storage of inorganic carbon and phosphorous in Mn carbonate phases would have had a substantial influence on biogeochemical carbon cycling during the Cryogenian.

Insights into multi-pathway peroxymonosulfate activation by copper-doped Ca/Mn perovskite oxides for diethyl phthalate degradation

Peroxymonosulfate (PMS) activation based on metallic catalysts with versatile mineral structures and superior catalytic properties has attracted much attention. In this study, we built a CaMnO3(CMO) with copper dopped to promote PMS activation by Mn(III)/Mn(IV) and Cu(I)/Cu(II) redox cycles with the synergistic effect of bimetal for efficient degradation of diethyl phthalate (DEP). Under optimal conditions, 95.7% of DEP (10 mg L−1) degradation was realized in 60 min, and the mineralization reached 75%, while only 26.9% of DEP was removed with little TOC removal by CaMnO3. Unexpectedly, not only •OH, O2•− and SO4•−, but also nonradical pathway singlet oxygen (1O2) was found to be involved in the CMO-Cu/PMS system. The redox cycles of Mn(III)/Mn(IV) and Cu(I)/Cu(II) effectively promoted PMS activation to reactive oxygen species (ROS), which were responsible for DEP degradation. Furthermore, density functional theory (DFT) calculations and liquid chromatograph-mass spectrometer (LCMS) were combined to explore the degradation pathway. This work provides a new insight for developing heterogeneous perovskites for PMS activation to construct more efficient method for water treatment.

Biogeochemical cycling of dissolved manganese in the Arabian Sea

The study of marine biogeochemical cycling of Mn, a bio-essential trace metal, is crucial to decipher its relative role in controlling the production and diversity of marine phytoplankton. Furthermore, Mn oxides and oxyhydroxides act as sinks for other trace elements in the water column, and Mn redox cycling may exert a major control on the vertical distribution of these elements. Dissolved Mn (dMn) concentrations are measured along two GEOTRACES-India (GI) transects, GI05 and GI10, for a basin-wide investigation of biogeochemical controls on the dMn distribution in the Arabian Sea (AS). Surface dMn distribution shows a strong spatial gradient, with relatively dMn-rich levels in the eastern AS (3.4–5.7 nmol kg−1) compared to the central and western AS (1.2–2.3 nmol kg−1). This correlates with the higher model estimates of soluble Mn input from the atmospheric dust deposition in the eastern AS (∼1.5–2.0 times of input in the western and central AS), and probable additional Mn input from riverine discharge and shallow shelf region of the eastern AS. In the south-eastern AS, a correlated increase in surface dMn with a decrease in salinity indicates the Mn input by the advection of dMn-rich, low-salinity Bay of Bengal (BoB) surface waters to the AS under the influence of the Northeast Monsoon Current. Our mass balance estimates for dMn in the euphotic waters (upper 100 m) suggest important contributions from atmospheric Mn deposition (14–99% of the total estimated input flux), and dMn input/dilution (13–74% of the total estimated input or removal flux) due to lateral/vertical advective-eddy diffusive mixing. Mn-oxidation and passive scavenging are determined to be the dominant processes for the dMn removal (61–99%) from the euphotic zone (upper 100 m), while export via Mn bio-assimilation is comparatively negligible.In the AS denitrification zone, the observed dMn maxima in the upper thermocline depths (∼200–400 m) result from the in situ reductive dissolution of Mn oxides and oxyhydroxides, and lateral advective-eddy diffusive Mn flux from the reducing sediments of the western Indian margin. Outside the denitrification zone, in the northern and western AS, a shift of dMn maxima to the lower thermocline waters (∼500 m) indicates the change in the source region and dMn input from the reducing margins of the north (Pakistan Margin) and north-western AS (Oman Margin), intersecting the core of the oxygen minima at the depth range of 400–600 m.Deep water (>1500 m) dMn concentrations are low (<0.3 nmol kg−1) in most of the AS regions. Anomalous dMn enrichment in the deep waters is observed in the southern and western AS, presumably indicating the influence of hydrothermal plumes emanating from the active hydrothermal vents over the Carlsberg Ridge and spreading ridges in the Gulf of Aden. A correlated and localized increase in dMn and dAl levels close to the Murray Ridge hints at dMn input from the sediment resuspension over the ridge and subsequent Mn dissolution in low-oxygen waters (DO < 20 µM) and/or diffusive flux from the Mn-rich pore waters.

Dual redox cycles of Mn(Ⅱ)/Mn(III) and Mn(III)/Mn(IV) on porous Mn/N co-doped biochar surfaces for promoting peroxymonosulfate activation and ciprofloxacin degradation

Mn and N co-doped biochar (Mn-N-TS) was prepared as an effective catalyst to activate peroxymonosulfate (PMS) for ciprofloxacin (CIP) degradation. As opposed to Mn-TS and N-TS, Mn-N-TS had more active sites containing N and Mn, as well as a greater specific surface area (923.733 m2 g−1). The Mn-N-TS exhibited excellent PMS activation ability. In the Mn-N-TS/PMS system, the CIP removal efficiency was 91.9% in 120 min. Mn and N co-doping could accelerate electron transfer between CIP and PMS molecules. Simultaneously, defect sites, graphitic N, pyridinic N, C═O groups, and Mn(II)/Mn(III)/Mn(IV) redox cycles acted as active sites to activate PMS and generate free radicals (OH, SO4− and 1O2). Furthermore, the Mn-N-TS/PMS system could effectively degrade CIP in a wide pH range, background substances, and actual water. Finally, a probable mechanism of PMS activation by Mn-N-TS was proposed. In conclusion, this work gave a novel direction for the rational design of Mn and N co-doped biochar.

Manganese redox cycling in immobilized bioreactors for simultaneous removal of nitrate and 17β-estradiol: Performance, mechanisms and community assembly potential

The application of bio-manganese (Mn) redox cycling for continuous removal of contaminants provides promise for addressing coexisting contaminants in groundwater, however, the feasibility of constructing Mn redox cycling system (MCS) through community assembly remains to be elucidated. In this study, Mn-reducing strain MFG10 and Mn-oxidizing strain MFQ7 synergistically removed 94.67 % of 17β-estradiol (E2) within 12 h. Analysis of potential variations in Mn oxides suggested that MCS accelerated the production of reactive oxygen species (ROS) and Mn(III), which interacted to promote E2 removal. After continuous operation of the Mn ore-based immobilized bioreactor for 270 days, the experimental group (EG) achieved average removal efficiencies of 89.63 % and 97.57 % for NO3−-N and E2, respectively. High-throughput sequencing results revealed complex symbiotic relationships in EG. Community assembly significantly enhanced the metabolic and physiological activity of the bioreactor, which promoting the expression of core functions including nitrogen metabolism, Mn cycling and organic matter resistance.

Synthesis, characterization and superoxide dismutase activity of a biomimetic Mn(III) complex covalently anchored to mesoporous silica

A mononuclear Mn(III) complex of a clickable ligand, [Mn(hbpapn)(H2O)2]ClO4·4.5H2O, where H2hbpapn = 1,3-bis[(2-hydroxybenzyl)(propargyl)amino]propane, has been prepared and fully characterized. The complex catalyzes the dismutation of superoxide employing a Mn(III)/Mn(IV) redox cycle, with catalytic rate constant of 3.9 × 106 M−1 s−1 determined through the nitro blue tetrazolium photoreduction inhibition assay, in aqueous medium of pH 7.8. The alkyne function of the ligand was used for the covalent attachment of the catalyst to azide modified mesoporous silicas with different texture and morphology, through click chemistry. In these materials the catalyst is essentially linked to the inner pore walls, isolated and protected from the external medium. The hybrid materials can be recycled, and retain or improve the superoxide dismutase activity of the free catalyst with the pore size of the solid matrix playing a role on the activity of the catalyst.

Microbially-mediated Mn redox cycling and Mn carbonate precipitation in the Marinoan glacial aftermath, South China

Carbonate-type Mn deposits developed at the top of the Ediacaran Doushantuo Formation (Marinoan glacial aftermath) along the northern margin of the Yangtze Block, South China, provide an exceptional opportunity to study Mn redox cycling in deep time, which remains a controversial topic of Mn biogeochemistry. To address this issue, here we conduct integrated petrological and geochemical work. Results show that Mn oxidizing microorganisms may fix CO2 into organic matter by oxidizing Mn(II). This process provides energy for metabolism of the microorganisms under obligatory oxidation conditions in natural geological environments. At the same time, Mn(II) is oxidized to unstable todorokite, with accompanying Co and Ce oxidation and enrichment. Under suboxic conditions, heterotrophic Mn-reducing bacteria use organic matter as an electron donor and Mn bio-oxide as a terminal electron acceptor to generate Mn(II) and 12C-rich dissolved inorganic carbon (DIC; carbonate and/or bicarbonate). Furthermore, microorganisms and macroalgae also provide nucleation sites for the precipitation of Mn carbonate minerals with structures consistent with microbially precipitated carbonates. Spherical and ellipsoidal Ca-rich rhodochrosite was formed in the syngenetic stage and cemented by Mg-rich kutnohorite in the early diagenetic stage. Microorganisms thus play an important role in Mn redox cycling and precipitation of Mn carbonate minerals, in a possibly universal phenomenon in geological evolution. The bloom of microorganisms and associated formation of mineral deposits may be a general phenomenon in the aftermath of a glaciation.

Mn2O3@Mn5O8 as an efficient catalyst for the degradation of organic contaminants in aqueous media through sulfite activation

Less-toxic, cost-effective, stable, and highly efficient catalysts for sodium sulfite (S(IV)) activation are required to degrade organic pollutants from wastewater. Herein, we report the facile thermal synthesis of Mn2O3@Mn5O8 that activates S(IV) more efficiently than other Mn and transition-metal oxides. Mn2O3@Mn5O8 exhibits good performance and long-term stability for eliminating various contaminants from aqueous media, including phenol, bisphenol A, nitrobenzene, 2,4-dichlorophenol, and acetaminophen. Its high performance is attributed to its multivalency, unique architecture, surface hydroxyl groups (–OH), and high surface area. X-ray diffractometry and high-resolution transmission electron microscopy revealed that Mn2O3@Mn5O8 comprises well-combined cubic Mn2O3 and monoclinic Mn5O8 crystalline structures, whereas electron paramagnetic resonance spectroscopy and scavenging tests showed that SO5•−, SO4•−, and •OH radicals are generated during S(IV) activation, with SO3•− as a precursor. The mixed-valence state provides effective and favorable electron transfer via Mn redox cycling (Mn(II) ↔ Mn(III) ↔ Mn(IV)), improving the S(IV) activation performance and catalytic activity. Mn2O3@Mn5O8/S(IV) system shows stable performance in the 3.0–7.0 pH range. Density functional theory calculations confirmed the higher catalytic activity as indicated by high –OH adsorption energy and significant inter-charge transformation. This study provides new insights and strategies for the activation of S(IV) using less-toxic metal oxides as catalysts and broadens the scope of heterogeneous Mn-based catalysts and S(IV) chemistry in real-world applications, particularly for the treatment of wastewater.

Synergistic activation of peroxymonosulfate between Co and MnO for bisphenol A degradation with enhanced activity and stability

In this work, a novel material of Co Nanoparticles anchored on MnO nanorods wrapped in carbon layers (Co/MnO-X@C) is successfully synthesized and applied to activate peroxymonosulfate (PMS) for Bisphenol A (BPA) degradation. More than 98% of BPA is removed by Co/MnO-0.32@C within 1 min. The reaction rate constant of Co/MnO-0.32@C (3.516 min−1) is much larger than Co@C (1.076 min−1) and MnO@C (0.006 min−1). The leached Co ions from Co/MnO-0.32@C (0.97 mg/L) is only 1/5 of Co@C (4.96 mg/L) after the catalytic reaction. The high activity and low leaching rate of Co indicate the synergistic effect between Co and MnO during PMS activation. Density functional theory (DFT) calculations reveal MnO modified with Co is favorable for the adsorption and activation of PMS and the release of reactive oxidation species (ROSs). The XPS results indicate the presence of Co(III)/Mn(II) redox cycle, while the generated Co(II) and Mn(III) is used for PMS activation, thus proving the synergistic effect further. The open circuit potential (OCP) test proves the direct electron-transfer (DET) exists on the surface of Co/MnO-X@C. Therefore, both radical and nonradical processes are present in the (Co/MnO-0.32@C)/PMS system. This work provides effective materials and synergistic theory between Co and MnO for environmental remediation.

Oxidative dissolution of Sb2O3 mediated by surface Mn redox cycling in oxic aquatic systems

Antimony trioxide (Sb2O3) is one of the primary forms of Sb in the environment, and its dissolution significantly impacts the migration and bioavailability of Sb. However, the dissolution of Sb2O3 coupled with abiotic redox of Mn processes is unclear. Here, we investigated the kinetics of Sb2O3 dissolution in the presence of the ubiquitous Mn(II) by kinetic experiments, spectroscopies, density functional theory calculations and the chemical kinetic modeling. The oxidative dissolution of Sb2O3 was catalyzed by Mn(II) through the in-situ generated amorphous Mn oxides (MnOx) under oxic conditions, during which the generation of Mn(III) is a critical step in Sb(V) release. The released Sb(V) was partially retained on MnOx through bidentate-binuclear (corner-sharing) complexes as revealed by extended X-ray absorption fine structure analysis. The coexistent morphological forms of Sb2O3, i.e., senarmontite and valentinite exhibited distinct dissolution patterns. Valentinite showed higher activity in catalyzing Mn(II) oxidation and faster oxidative dissolution than senarmontite, due to its higher surface energy and lower conduction band minimum of its exposed facets. These abiotic processes can extrapolate to other metal(loid)s (hydr)oxides, further supplying for the comprehensive understanding of the redox transformation of Mn

Insights into the multiple roles of Ca2+ ion in peroxymonosulfate activation over Mn2O3 for organic pollutants degradation

The development of efficient and eco-friendly catalysts for peroxymonosulfate (PMS) activation is highly desired for pollutants removal in wastewater. Recently calcium ion (Ca2+) has been recognized to promote the catalytic performance of Mn oxides by enhancing the oxidizing power of PMS. However, the impact of pollutants types and influence of solution pH on the catalyst-oxidant interaction towards Ca2+ promotion have not been considered until now. This study investigated the effect of Ca2+ for pollutant degradation by Mn2O3 activated PMS system, with various factors considered in detail such as the dose of Ca2+, pKa of organic pollutants, and solution pH. To deepen the understanding of the formation of Mn2O3/PMS complex in the presence of Ca2+, XPS, ATR-FTIR, radical scavenging, EPR, as well as PMS decomposition experiments, were analyzed. The binding of Ca2+ on the surface of Mn2O3 efficiently promoted PMS decomposition and accelerated the redox cycles of Mn(III)/Mn(IV) with a faster rate for the production of HO• and 1O2. Ca2+ also enriched the pollutants with negative charges around the catalyst to speed up the degradation process. This work points out a novel thought on the improvement of the PMS activation system with nonreducible metal ions.