Manganese Carbonate Research Articles

Uncovering fantastic synergistic lithium adsorption with manganese-titanium based composite nanospheres: Mild synthesis and molecular dynamics simulation insights

In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains, conventional lithium extraction methods have been proven inadequate due to their limited production capacity and high operational costs. This work introduces a novel approach to the manganese-titanium based composite HMTO (Mn:Ti=1:4) lithium ion-sieve (LIS) nanospheres, employing lithium acetate dihydrate, manganese carbonate and titanium dioxide P25 as the primary materials. These nanospheres exhibit relatively uniform spherical morphology, narrow size distribution, small average particle size (ca. 55 nm), large specific surface area (43.58 m2 g−1) and high surface O2− content (59.01%). When utilized as the adsorbents for Li+ ions, the HMTO (Mn:Ti=1:4) LIS demonstrates a fast adsorption rate, approaching equilibrium within 6.0 h with an equilibrium adsorption capacity (qe) of 79.5 mg g−1 and a maximum adsorption capacity (qm) of 87.26 mg g−1 (initial concentration C0: 1.8 g L−1). In addition, the HMTO (Mn:Ti=1:4) also delivers a high lithium extraction from the simulated high magnesium-lithium molar ratio salt lake brine (Mg:Li=103), achieving a qe of 33.85 mg g−1 along with a remarkable selectivity (αMgLi=2192.76). Particularly, the HMTO (Mn:Ti=1:4) LIS showcases a satisfactory recycling adsorption performance. The adsorption capacity remains at a high level, even that determined after the 5th cycle (55.45 mg g−1) surpasses that of the most recently reported adsorbents. Ultimately, the fantastic synergistic lithium adsorption mechanism is deliberately uncovered by leveraging the ion exchange principles and molecular dynamics (MD) simulations.

Electrodeposited manganese carbonate as an electrocatalyst for hydrogen evolution reaction in acidic medium

The electrolysis of water is the key method for hydrogen production but the high overpotential necessitates electrocatalysts. Traditionally, Pt is used, but it is scarce and costly. Herein, MnCO3 is unveiled as an electrocatalyst for the production of hydrogen. MnCO3 is electrodeposited onto pencil graphite by chronoamperometric method and confirmed by XRD and vibrational spectroscopic studies. MnCO3 electrodeposited for 15 min at 2 V demonstrates a good HER activity (overpotential of 123 mV to reach 10 mA cm−2) in 0.5 M H2SO4 with a Tafel slope of 79 mV dec−1. In addition, MnCO3 exhibited good stability during continuous operation (over 3000 cycles and 14 h). Though MnCO3 requires higher overpotential than the benchmark catalyst (Pt/C) to reach 10 mA cm−2, it outperforms Pt/C at higher current density (≥75 mA cm−2) demonstrating that MnCO3 could be used as an electrocatalyst to produce H2 at a high rate from acidic medium.

Mechanosynthesis of pseudocapacitive MnCO3 and CoCO3 electroactive materials

Transition metals are known for their enormous potential as electrode materials for supercapacitor applications, however anhydrous carbonate minerals, namely Mn-carbonate, and Co-carbonate, are less explored and exhibit competitive energy storage performance compared to oxide and hydroxide forms. For the first time, MnCO3 (Rhodochrosite), CoCO3 (Spherocobaltite) and MnCo mixture (Mn1-xCoxCO3) were synthesized via mechanochemistry by a one-pot approach and used to prepare pseudocapacitive electrode materials for electrochemical energy storage. In this work, these materials were tested in alkaline electrolyte, and the morphological and structural features of the materials were examined using SEM (Scanning Electron Microscope), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). The surface composition was studied by X-ray photoelectron spectroscopy (XPS). After milling, the microstructures showed an increase in dislocations and microstrains in their crystal lattices which influenced the electrochemical performance. The crystallinity of the carbonate materials was also affected by grinding. In 1 M KOH electrolyte, milled MnCO3 evidenced the highest specific capacitance (354.3 F/g at 1.0 A/g), while milled CoCO3, revealed impressive capacitance retention of 94.8 % after 20000 continuous charge–discharge cycles at 10 A/g. Interestingly, the composite (Mn-Co)CO3 evidenced superior rate capability (58.8 %) and enhanced capacitance retention under cycling compared to the individual cobalt and manganese carbonates. The results evidence the excellent electrochemical behavior of Mn and Co carbonates prepared by a simple, low-cost, and green route and prove their potential as electroactive electrode materials for electrochemical energy storage applications, particularly pseudocapacitors.

Investigating the Dewatering Efficiency of Sewage Sludge with Optimized Ratios of Electrolytic Manganese Residue Components.

As an industrial waste residue, Electrolytic Manganese Residue (EMR) can greatly promote sludge dewatering and further particle-size optimization can significantly strengthen sludge dewaterability. In this study, the effects of ammonium sulfate, calcium sulphate dihydrate, and manganese carbonate in EMR on sludge dewatering performance were investigated using the response surface optimization method. It was found that the optimized ratio of three components in EMR was 1.0:1.6:2.2 based on capillary suction time (CST), specific resistance of filtration (SRF), and zeta potential of dewatered sludge. The composition ratio of particle-size optimized EMR was modified based on the above optimization, resulting in a significant increase in sludge dewatering performance (CST and SRF reduced by 8.7% and 11.2%, respectively). Compared with those in original sludge, the content of bound extracellular polymeric substances in the conditioned sludge with optimized ratio was drastically reduced while that of soluble extracellular polymeric substances was slightly increased, which was in accordance with the decline of fluorescence intensity. These findings indicated the disintegration of extracellular polymeric substances, the enhancement of hydrophobicity, and dewatering properties of the sludge. In summary, optimized EMR can effectively intensify the dewaterability of sludge, providing a competitive solution for dewatering and further disposal of sludge.

Removal and stabilization of As and Cd in water/soil using silicate-supported nano zero-valent iron composites: Preparation, behavior, mechanism and cost analysis

A novel silicate-supported nano zero-valent iron composite material (nZVI@SS) for the removal and stabilization of arsenic (As) and cadmium (Cd) in water/soil had been developed through the modification of low-grade oolitic iron ore (OI) by reduction, while refinery sludge (RS) as reductant, manganese carbonate (MC) as additive in this work. The As and Cd adsorption capacity of nZVI@SS reached 93.91 mg·g−1 and 265.81 mg·g−1, respectively. Its specific surface area and pore volume increased by 19.28 m2·g−1 and 0.24 cm3·g−1, respectively when compared with unmodified OI. In the actual soil leaching process, using 2 % nZVI@SS for 30 days, the leaching concentrations of As and Cd decreased by 87.86 % and 85.51 % respectively, while their bioavailable contents were reduced by 15.59 mg·kg−1 and 1.40 mg·kg−1, correspondingly. The formation of chemical precipitates as Fe-As, Ca-As compounds, and Cd(OH)2 was the main mechanism of their adsorption process. Therefore, HMs adsorbed by nZVI@SS were difficult to desorb, making it more suitable for passivation/stabilization of HMs in groundwater/soil. Furthermore, the production cost of nZVI@SS was approximately 50 $/T, below the average market value of comparable adsorption materials. This method made low-grade minerals into environmentally friendly materials with high added value, significantly reduced the environmental risk of HMs in water/soil, and provided a new approach for the development of sustainable environmentally friendly materials using hazardous waste RS as a resource.

Manganese carbonate superparticles as DNA- and pH-responsive magnetic resonance imaging contrast agents

Manganese carbonate nanoparticles (NPs) have been developed as pH-triggered responsive magnetic resonance imaging (MRI) contrast agents for tumor diagnosis, but the signal amplification of MRI is still limited due to the lack of response to other pathological parameters of tumors. Here, random single-stranded deoxyribonucleic acid (ssDNA) was explored as a biomimetic template to prepare manganese carbonate superparticles (MnCO3 SPs) assembled from ultrasmall particles. We focused on the degradation ability of DNA-MnCO3 SPs triggered by DNA and its trigger mechanism. The results show that different sequences of DNA could trigger the disassembly of these DNA-MnCO3 SPs and result in MR signal amplification. Further investigations show the DNA-MnCO3 SPs possess good physiological stability, but increased degradation sensitivity under dual triggering of DNA and low pH. In vivo MR and FL dual-modal imaging for tumor region display T1-signal rapid amplification, suggesting rapid responsiveness of DNA-MnCO3 SPs to DNA. Therefore, the design of DNA- and pH-triggered DNA-MnCO3 SPs may provide a new idea for the construction of next-generation activatable contrast agents with high specificity and high sensitivity.

Microbial contribution to the formation of the Carboniferous sedimentary manganese deposits in northwestern China

There is an increasing consensus that microbes play a critical role in the genesis of sedimentary manganese (Mn) carbonate deposits. However, compelling evidence for the microbial involvement during sedimentary Mn metallogenesis remains insufficient, and the specific effects of microbial mediation need to be further elucidated. To advance our understanding of the microbial Mn metallogenesis, multi-scale petrographic observations and high-resolution mineralogical analyses (mainly based on Fourier transform infrared spectrometer and Raman spectroscopy) were conducted on the Carboniferous black shale-hosted Malkansu and limestone-hosted Zhaosu Mn ore deposits in northwestern China. Results show that the Mn ore samples are characterized by finely laminated texture with μm-scale cyclic variations of microbe-associated minerals including rhodochrosite, apatite, quartz, and organic matter as well. These features indicate the ubiquity of microbial mats during Mn mineralization. Microbial involvement is also supported by Mn carbonate aggregates with variable morphologies (filamentous with pearl necklace-like inner forms resembling vermiform morphologies and spheroidal, coccoid-like forms), as well as the annular organic matter that resembles bacterial cells. The cyclic occurrence of trace amounts of remnant Mn oxides verify that primary Mn accumulation took place under oxic bottom waters. The negative co-variation between Mn carbonates and organic matter on Raman profiles suggests that the former was formed during diagenesis via organic matter decomposition coupled with Mn oxide reduction. Combined with previous experimental simulations and natural observations, a two-step microbially mediated Mn metallogenic model is tentatively proposed for the studied Mn deposits: (1) Mn(II)-oxidizing bacteria effectively catalyzed the deposition of considerable Mn oxides under oxygenated bottom water columns, a process that was simultaneously sustained by oxygenic microbial mats such as cyanobacteria; (2) Buried Mn oxides were reduced by highly reactive organic matter sourced from dead biomats of Mn(II)-oxidizing bacteria and benthic phototrophs, a process mediated by Mn(IV)-reducing bacteria which not only promoted the reaction rate but also served as nucleation sites for Mn carbonate minerals. This model can also help to explain the occurrence of diverse authigenic accessory minerals (e.g., quartz, apatite, and talc) and remarkable enrichments of several specific elements (e.g., Co, Ce, and Mo) in the studied Mn ores, which were closely linked to the decomposed cells and extracellular polymeric substance (EPS). By comparing with previous microbial investigations on Mn deposits over geological history, we further highlight the fundamental role of microorganisms in regulating the formation of economic Mn carbonate deposits.

Synergistic denitrification and Mn cycle driven by sulfur autotrophy significantly enhanced nitrogen removal

Due to the low C/N and high NO3−-N content in tailwater of wastewater treatment plants, the need for further denitrification treatment attracted wide attention. To achieve deep denitrification of tailwater with low C/N and high NO3−-N, a novel sulfur-manganese carbonate ore denitrification (SMCD) biological reactor was constructed. The denitrification performance of SMCD reactor was significantly higher than that of sulfur denitrification and manganese carbonate ore denitrification reactors. Across the study, the removal efficiencies of TN and NO3−-N were above 90%, and without NO2−-N accumulation in the SMCD reactor. Quantitative results of functional genes showed that SMCD reactor were conducive to realize complete denitrification. Besides, manganese autotrophic denitrification (MAD) process occurred in the SMCD reactor. By analyzing the nitrogen as well as SO42- and Mn(Ⅱ) concentrations along the height, it was found that the conversion between Mn(II) and Mn(IV) was stable during Stage Ⅲ (C/N=1). The microbiota in the SMCD reactor was distinctly different from that in the controls. Thiobacillus, Thermomonas, and an unclassified member in family cvE6 were the dominant members of SMCD reactor. Besides, Thermomonas, Dokdonella, and Simplicispira were identified as potential Mn oxidizers. The SMCD reactor exhibited a significant synergistic denitrification effect by coupling sulfur autotrophic denitrification and MAD process, which provided an effective solution for the deep denitrification of low C/N tailwater.

Hydrogeochemical analysis of groundwater quality during the pre- monsoon season of Manipur, India

ABSTRACT The water quality index (WQI) and irrigational index for groundwater were studied in the northeastern section of the Manipur Valley in northeast India. Water samples were collected in 2022 during the pre-monsoon season. To compute the water quality index for drinking water, the basic chemical parameters of total hardness, pH, electrical conductivity, total dissolved solids, Calcium, Sodium, Iron, Magnesium, Manganese, Chlorine, and Hydrogen Carbonate were used. The assessment of bacteriological quality is also done, which is crucial for overall water quality evaluation, alongside physical and chemical analyze. For determining irrigation suitability, irrigational indices such as sodium absorption ratio, sodium percentage, and magnesium hazard were calculated. WQI, %Na+, Sodium Adsorption Ratio (SAR), magnesium hazard, permeability Index and total hardness indicate that most water samples are harmless for irrigation and drinking purpose. They have affirmative relationships indicating that these characteristics are interdependent. Approximately 25% of the Piedmont zone groundwater is found to be unfit for agricultural and drinking usage. The encrustation of gypsum, halite, and evaporation into the Disang shares accelerate the dissolution of ions in Piedmont water, resulting in quality degradation. According to Gibbs plots, Durov Scatter Plot, and Hill Piper Trilinear Diagram of water dominated the rock-weathering process, while hydrochemical facies progressed from the beginning to the intermediate stage of Chadha’s graphical representation illustrates the progression of hydrochemical processes in surface water. Therefore, proper integrated water resource management and development are required for effective water resource utilization, particularly around the Piedmont zone. In recent years, the quality of groundwater has caused a significant deal of alarm, and an increasing number of studies relating to it have been published. The geological, structural, and geomorphological features in the intermontane Imphal Valley in Manipur, India, were identified using SRTM DEM data by QGIS Software. This area has simple geology and structural elements, making it an appropriate site to evaluate the use of remote sensing and GIS tools in geological studies. To prevent a water crisis, groundwater resources must be managed sustainably. The current study also concentrated on a bibliometric examination of groundwater management and access to gauge the state of the field. A bibliometric examination of these papers may offer insight into current research and trends. We are the first to join Groundwater Quality Assessment with bibliometric analysis. This prediction, if taken into consideration strategically during the planning of preventive measures for groundwater quality can help to analyze future evaluation to a great extent.

Controls on the formation of Mn carbonates in mudrocks of the Datangpo Formation, Northern Margin Rift Basin, Yangtze Block

Deglaciation following the Sturtian Ice Age led to widespread manganese carbonate precipitates within marine mudrocks, reflecting unique climatic and oceanographic changes. The Mn carbonates hold economic importance in the Datangpo Formation, Yangtze Block, South China. Although their genesis in the Nanhua Rift Basin is well understood, little is known regarding their formation mechanism in the North Margin Rift Basin (NMRB). With growing interest in Mn ore exploration in this region, this study examines the weathering trend, climate patterns and watermass conditions using a variety of geochemical proxies. The results reveal two phases of climate variation during the deglaciation. Climate during the early phase (Phase I) was unstable, characterized by fluctuating values of Chemical Index of Alteration (CIA = 65 ± 4) and elevated Li isotope (8.8 ± 3.0‰) patterns. The degree of chemical weathering during the later stage (Phase II) was relatively stable (CIA = 65 ± 1, δ7Li = 5.4 ± 2.7‰), but the weathering intensity increased due to the reduced denudation rate, possibly related to a shift in the basin development. Fe speciation data indicate euxinia prevailing much of the section. However, Mo and U enrichment (> 1) and fluctuating ratios of Mo versus total organic content (0–40) suggest that pulses of freshwater influx associated with climate variation during Phase I caused the fluctuation of the chemocline along the continental shelf, facilitating the formation of Mn carbonates through the particulate Fe-Mn-hydroxide shuttle. With the establishment of stabilized climate, basin tectonics, and watermass circulation during Phase II, the accumulation of Mn carbonates in the sediments became less significant. The accumulation of Mn carbonates in the NMRB conforms to the “bathtub ring model”, distinct from the metallogenic model in the NRB, providing valuable guidance for Mn ore prospecting within this area and elsewhere with similar settings.

Effect of Magnesium Site Doping on Electrochemical Properties of Mg-Mn Composite Materials and Application of Carpet-Like Sheets Composite Formed by Cr Doping in Aqueous Zinc-Ion Batteries

Manganese based compounds have very stable electrochemical properties, thus they are widely applied in aqueous zinc-ion battery. However, it is easy to dissolve manganese in the process of charge and discharge, which leads to the collapse of the cathode material structure. In this paper, the composite materials of manganese carbonate and magnesium carbonate were synthesized by hydrothermal method, and its properties were optimized by doping modification. According to the electrochemical tests, the electrochemical performance of the material synthesized with 5% Cr doping is relatively stable. Moreover, with the increase of Cr content, the charge transfer impedance of the material can be significantly reduced. In the cyclic tests, after 60 cycles of charge and discharge under different current densities, and another several cycles at the current density of 50 mA g−1, the capacity rises to 212.01 mAh g−1, higher than the first discharge capacity. SEM tests are also conducted to survey the micro-structure of the material, besides the cube unit, there are also carpet-like sheets made of nano-sized joined petal-like unit, which greatly increases the specific surface area of the material. According to the data of EDS and XPS, the fact that that the types and valence states of elements in the composites were consistent with those in manganese carbonate and magnesium carbonate are confirmed. Through the infrared and Raman tests, the functional groups in the synthesized material are proven to correspond to the molecular formula. From the XRD pattern, no obvious impurity peaks can be observed. With all the data obtained from physical characterization, it can be concluded that the material is mainly composed of manganese carbonate and magnesium carbonate.

Platelet Membrane Biomimetic Manganese Carbonate Nanoparticles Promote Breast Cancer Stem Cell Clearance for Sensitized Radiotherapy.

The presence of cancer stem cells (CSCs) significantly limits the therapeutic efficacy of radiotherapy (RT). Efficient elimination of potential CSCs is crucial for enhancing the effectiveness of RT. In this study, we developed a biomimetic hybrid nano-system (PMC) composed of MnCO3 as the inner core and platelet membrane (PM) as the outer shell. By exploiting the specific recognition properties of membrane surface proteins, PMC enables precise targeting of CSCs. Sonodynamic therapy (SDT) was employed using manganese carbonate nanoparticles (MnCO3 NPs), which generate abundant reactive oxygen species (ROS) upon ultrasound (US) irradiation, thereby impairing CSC self-renewal capacity and eradicating CSCs. Subsequent RT effectively eliminates common tumor cells. Both in vitro cell experiments and in vivo animal studies demonstrate that SDT mediated by PMC synergistically enhances RT to selectively combat CSCs while inhibiting tumor growth without noticeable side effects. Our findings offer novel insights for enhancing the efficacy and safety profiles of RT.

Mn2+ recycling in hypersaline wastewater: unnoticed intracellular biomineralization and pre-cultivation of immobilized bacteria.

Microbially induced manganese carbonate precipitation has been utilized for the treatment of wastewater containing manganese. In this study, Virgibacillus dokdonensis was used to remove manganese ions from an environment containing 5% NaCl. The results showed a significant decrease in carbonic anhydrase activity and concentrations of carbonate and bicarbonate ions with increasing manganese ion concentrations. However, the levels of humic acid analogues, polysaccharides, proteins, and DNA in EPS were significantly elevated compared to those in a manganese-free environment. The rhodochrosite exhibited a preferred growth orientation, abundant morphological features, organic elements including nitrogen, phosphorus, and sulfur, diverse protein secondary structures, as well as stable carbon isotopes displaying a stronger negative bias. The presence of manganese ions was found to enhance the levels of chemical bonds O-C=O and N-C=O in rhodochrosite. Additionally, manganese in rhodochrosite exhibited both + 2 and + 3 valence states. Rhodochrosite forms not only on the cell surface but also intracellularly. After being treated with free bacteria for 20days, the removal efficiency of manganese ions ranged from 88.4 to 93.2%, and reached a remarkable 100% on the 10th day when using bacteria immobilized on activated carbon fiber that had been pre-cultured for three days. The removal efficiency of manganese ions was significantly enhanced under the action of pre-cultured immobilized bacteria compared to non-pre-cultured immobilized bacteria. This study contributes to a comprehensive understanding of the mineralization mechanism of rhodochrosite, thereby providing an economically and environmentally sustainable biological approach for treating wastewater containing manganese.

Novel synergistically effects of palladium-iron bimetal and manganese carbonate carrier for catalytic oxidation of formaldehyde at room temperature

The elimination of formaldehyde at room temperature holds immense potential for various applications, and the incorporation of a catalyst rich in surface hydroxyl groups and oxygen significantly enhances its catalytic activity towards formaldehyde oxidation. By employing a coprecipitation method, we successfully achieved a palladium domain confined within the manganese carbonate lattice and doped with iron. This synergistic effect between highly dispersed palladium and iron greatly amplifies the concentration of surface hydroxyl groups and oxygen on the catalyst, thereby enabling complete oxidation of formaldehyde at ambient conditions. The proposed method facilitates the formation of domain-limited palladium within the MnCO3 lattice, thereby enhancing the dispersion of palladium and facilitating its partial incorporation into the MnCO3 lattice. Consequently, this approach promotes increased exposure of active sites and enhances the catalyst's capacity for oxygen activation. The co-doping of iron effectively splits the doping sites of palladium to further enhance its dispersion, while simultaneously modifying the electronic modification of the catalyst to alter formaldehyde's adsorption strength on it. Manganese carbonate exhibits superior adsorption capability for activated surface hydroxyl groups due to the presence of carbonate. In situ infrared testing revealed that dioxymethylene and formate are primary products resulting from catalytic oxidation of formaldehyde, with catalyst surface oxygen and hydroxyl groups playing a crucial role in intermediate product decomposition and oxidation. This study provides novel insights for designing palladium-based catalysts.

An environmentally friendly approach for the extraction and recovery of Mn from pyrolusite by ammonium sulfate roasting‐water leaching and ammonium carbonate precipitation

AbstractWith the growth of the new energy industry, the requirements for manganese have increased significantly. In this paper, the method of manganese extraction from pyrolusite using ammonium sulfate roasting and water leaching was presented. At the optimal process parameters: mass ratio of (NH4)2SO4 to pyrolusite of 2:1, the roasting temperature of 420°,C and duration of 120 min, the leaching efficiency of Mn and Fe was 94.55% and 54.38%, respectively. The mechanism analysis shows that MnO2 and Fe2O3 in pyrolusite were converted to (NH4)2Mn2(SO4)3, (NH4)3Fe(SO4)3, and NH4Fe(SO4)2 by roasting with ammonium sulfate. Iron was removed from the leaching solution with the addition of ammonia. Afterward, manganese carbonate products were prepared from iron‐free manganese sulfate solution by adding ammonium carbonate at a stirring duration of 60 min, a reaction temperature of 40°C, a pH of 7, and a molar ratio of ammonium carbonate to the manganese of 1.1:1, the precipitation efficiency of manganese could reach 99.8%, and the obtained manganese carbonate products were compliant with the industry standards. The ammonia released during the roasting process could be absorbed to regenerate (NH4)2SO4 and the final filtrate after evaporation and crystallization could be used to recycle (NH4)2SO4, both of which were used again into roasting process to reduce the consumption of raw material. In this process, the roasting temperature was only 420°C, which was significantly lower than the pyrometallurgical process suggested in earlier studies.

Preparation of magnesium carbonate and manganese carbonate composite materials doped at manganese site by hydrothermal method and study of Co doping effect

Preparation of magnesium carbonate and manganese carbonate composite materials doped at manganese site by hydrothermal method and study of Co doping effect

Volcanism-driven lacustrine redox fluctuations were responsible for the formation of the Jehol Lagerstätte: Evidence from a high-resolution Aptian sedimentary core, Northeast China

While a “volcanic Pompeii” model is well accepted as the cause of mass mortality and exceptional preservation of the Jehol Biota, no consensus has been reached thus far regarding the cause of mass mortality of fossils found in interbedded finely laminated sediments. We propose that volcanically driven, lacustrine redox fluctuations were responsible for the formation of the Jehol Lagerstätte, based on data obtained from a new drill core of Lower Cretaceous sedimentary rocks in the Chaoyang Basin, Northeast China. We found manganese-rich carbonates are interbedded with molybdenum-rich black mudstones and tuffs, and phosphatized fossils in the drill core. The elemental enrichment factors for molybdenum are much higher than for uranium in the black mudstones, suggesting the role of the manganese particulate-shuttle in deposition of this element. The manganese-rich carbonates are formed by the reaction of manganese oxides with organic matter, indicating an oxidized water column. This process accelerates the enrichment of molybdenum under anoxic non-sulfidic conditions. The interbedded manganese carbonates and molybdenum-rich mudstones thus record redox fluctuations in the lacustrine depositional environment. Given the numerous tephra in the black mudstones and soft-sediment deformation structures ostensibly associated with seismicity, we propose that the redox fluctuations were caused by lake eutrophication and turnover driven by volcanism that was ultimately related to the destruction of the North China Craton. These volcanically induced redox fluctuations, along with the toxicity of the volcanic gases, may have caused the simultaneous mass mortality of aquatic, terrestrial, and avian fauna. Micro-X-ray fluorescence, energy dispersive X-ray spectroscopy, and Raman mapping show that the preservation of fossils was mainly due to phosphatization. Fluctuating redox conditions facilitated phosphate enrichment in sediments. Both the oxic and anoxic non-sulfidic conditions were conducive to the preservation of organisms by phosphatization, and oxidation was favorable for phosphate mineralization, both contributing to the exceptional preservation of the Jehol Biota fossils.

Study on the Electrochemical Properties of Mg1−xYxCO3@2MnCO3 Doped at Magnesium Site and the Effect of Manganese Carbonate and Magnesium Carbonate Composite Material Modified by Zn Doping

Mangan-based zinc ion batteries have received increasing attention due to their high theoretical capacity and environmental friendly properties. However, the capacity attenuation of manganese-based materials during the charge-discharge cycle seriously affects the improvement of electrochemical performance. In order to solve the problem of capacity attenuation, magnesium carbonate material was combined with manganese carbonate material, and the magnesium site was doped and modified. In this paper, the Mg0.98Zn0.02CO3@2MnCO3 material was selected out from all the synthesized materials due to its stable electrochemical performance, its capacity is as high as 283.65 mAh g−1 under the current density of 100 mA g−1. Subsequently, the characterization test was carried out to further discover the composition of the material. It can be observed from SEM that the material has two main structures: cube shape and spheroid shape, and nanowires grow on the surface of the cube structure. Moreover, the EDS and XPS tests were conducted which could prove the elements contained in Mg0.98Zn0.02CO3@2MnCO3 material were consistent with the valence states of the elements in manganese carbonate and magnesium carbonate. The further infrared and Raman tests showed that the functional groups in the material were also consistent with the molecular formula. According to the XRD test result, no obvious impurity peak can be oberved, indicating the electrochemical performance of Mg0.98Zn0.02CO3@2MnCO3 composite material synthesized by hydrothermal method is relatively stable.

Unraveling the importance of water ratio in direct lithium-ion battery cathode recycling

This study investigates the impact of water ratio on the direct aqueous recycling of NMC811. Three different ratios of NMC811 to water were examined. The results demonstrate that the water ratio significantly affects the electrochemical performance of NMC811. Capacity fading is observed in all water-exposed samples, with the sample having the lowest water ratio showing less fading compared to the samples processed with higher water ratios. Both samples with higher water ratios exhibit similar performance, suggesting an equilibrium at the NMC811-water interface is established. Characterization of the cathode materials reveals variations in the amount and type of surface species. The pristine sample, not exposed to water, only shows Li2CO3 and NiO as surface species, while the water-exposed NMC811 samples exhibit nickel carbonates and hydroxides along with associated water. The poorer performance of samples exposed to higher water ratios is likely due to higher amounts of these species forming on the particle surface. Additionally, lithium, cobalt, and manganese carbonates, as well as lithium hydroxide with associated water, are detected and could further contribute to the poorer performance.

Thermodynamic properties of titanium-manganite LaСаTiMnO6

By the method of dynamic calorimetry in the range of 298.15-673 K, the heat capacity of titanium-manganite LaСаTiMnO6, obtained by solid-phase interaction at 800-1200oC from lanthanum, titanium (II), manganese (III) and calcium carbonate oxides was studied. On the dependence curve Ср°~¦(T) in the specified temperature range, a λ-shaped effect was detected at 598 K, probably related to the phase transition of the second kind. A fundamental constant is determined — the standard heat capacity of LaСаTiMnO6, equal to 221±14 J /(mol×K). Its standard entropy, equal to 206±6 J/(mol×K), was estimated by the approximate method of ion increments. Based on experimental data, taking into account the temperature of the phase transition, the equations describing the temperature dependences of Ср°~¦(T) and the thermodynamic functions So (T), Ho (T) — Ho (298.15) and Фхх(Т) of the investigated titanium-manganite lanthanum and calcium are calculated. The standard heat capacity of LaСаTiMnO6 is also calculated using the Debye method, the value of which is in good agreement with experimental data. According to the developed methodology, the standard enthalpy of titanium-manganite formation was calculated, equal to — 3867.5 kJ/mol.