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Keywords = copper-manganese mixed oxides

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15 pages, 3882 KiB  
Article
Performance of Low-Cost Energy Dense Mixed Material MnO2-Cu2O Cathodes for Commercially Scalable Aqueous Zinc Batteries
by Gautam G. Yadav, Malesa Sammy, Jungsang Cho, Megan N. Booth, Michael Nyce, Jinchao Huang, Timothy N. Lambert, Damon E. Turney, Xia Wei and Sanjoy Banerjee
Batteries 2025, 11(8), 291; https://doi.org/10.3390/batteries11080291 - 1 Aug 2025
Viewed by 175
Abstract
Zinc (Zn)-based batteries have attracted significant interest for applications ranging from electric bikes to grid storage because of its advantageous properties like high abundance, non-toxicity and low-cost. Zn offers a high theoretical capacity of two electrons per atom, resulting in 820 mAh/g, making [...] Read more.
Zinc (Zn)-based batteries have attracted significant interest for applications ranging from electric bikes to grid storage because of its advantageous properties like high abundance, non-toxicity and low-cost. Zn offers a high theoretical capacity of two electrons per atom, resulting in 820 mAh/g, making it a promising anode material for the development of highly energy dense batteries. However, the advancement of Zn-based battery systems is hindered by the limited availability of cathode materials that simultaneously offer high theoretical capacity, long-term cycling stability, and affordability. In this work, we present a new mixed material cathode system, comprising of a mixture of manganese dioxide (MnO2) and copper oxide (Cu2O) as active materials, that delivers a high theoretical capacity of ~280 mAh/g (MnO2 + Cu2O active material) (based on the combined mass of MnO2 and Cu2O) and supports stable cycling for >200 cycles at 1C. We further demonstrate the scalability of this novel cathode system by increasing the electrode size and capacity, highlighting its potential for practical and commercial applications. Full article
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16 pages, 4896 KiB  
Communication
Fiber Fabry–Perot Sensor Based on Ion-Imprinted Sodium Alginate/Graphene Oxide Hydrogel for Copper Ion Detection Using Vernier Effect
by Ning Wang, Shiqi Liu, Liang Xu, Longjiao Wang, Ming He, Chuanjie Lei and Linyufan Xiao
Sensors 2025, 25(3), 920; https://doi.org/10.3390/s25030920 - 3 Feb 2025
Viewed by 991
Abstract
This work proposes an optical fiber copper ion sensor, which is fabricated by an ion-imprinted sodium alginate/graphene oxide (SA/GO) hydrogel and single-mode fiber (SMF). This sensing Fabry–Perot Interferometer (FPI) achieves −1.98 nm/(mg/L) sensitivity with 0.998 linearity. To achieve higher sensitivity, we add a [...] Read more.
This work proposes an optical fiber copper ion sensor, which is fabricated by an ion-imprinted sodium alginate/graphene oxide (SA/GO) hydrogel and single-mode fiber (SMF). This sensing Fabry–Perot Interferometer (FPI) achieves −1.98 nm/(mg/L) sensitivity with 0.998 linearity. To achieve higher sensitivity, we add a reference FPI to create a Vernier effect. We achieve 19.58 nm/mg/L sensitivity and 0.989 linearity at a concentration range of 0 mg/L–1.4 mg/L. It was 9.9 times higher than that of a single-sensing FPI. The experimental results also demonstrate that when the FSR values of two FPIs are closer, the higher response sensitivity is achieved. The sensor also has good measurement repeatability and dynamic response. In addition, the experimental results of response selectivity show that its response sensitivity to copper ions is significantly higher than other six types of ions, including iron ions, lead ions, magnesium ions, manganese ion, zinc ions, chromium ions. The copper ion is also mixed with six types of ions to deeply investigate the response selectivity. Good response selectivity and cross-responding are demonstrated by experimental results. Full article
(This article belongs to the Section Optical Sensors)
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14 pages, 11164 KiB  
Article
Photoelectron Spectroscopy Study of the Optical and Electrical Properties of Cr/Cu/Mn Tri-Doped Bismuth Niobate Pyrochlore
by Nadezhda A. Zhuk, Nikolay A. Sekushin, Maria G. Krzhizhanovskaya, Artem A. Selutin, Aleksandra V. Koroleva, Ksenia A. Badanina, Sergey V. Nekipelov, Olga V. Petrova and Victor N. Sivkov
Sci 2025, 7(1), 1; https://doi.org/10.3390/sci7010001 - 26 Dec 2024
Viewed by 956
Abstract
The multielement pyrochlore of the composition Bi1.57Mn1/3Cr1/3Cu1/3Nb2O9−Δ (sp. gr. Fd-3m:2, 10.4724 Å) containing transition element atoms—chromium, manganese and copper in equimolar amounts—was synthesized for the first time using the solid-phase reaction method. [...] Read more.
The multielement pyrochlore of the composition Bi1.57Mn1/3Cr1/3Cu1/3Nb2O9−Δ (sp. gr. Fd-3m:2, 10.4724 Å) containing transition element atoms—chromium, manganese and copper in equimolar amounts—was synthesized for the first time using the solid-phase reaction method. The microstructure of the ceramics is grainless and has low porosity. The sample is characterized by reflection in the red (705 nm) color region. The band gap for the direct allowed transition in the sample is 1.68 eV. The parameters of the Bi5d, Nb3d, Сr2p, Mn2p, and Cu2p X-ray photoelectron spectroscopy (XPS) spectra for the mixed pyrochlore are compared with the parameters of transition element oxides. For the complex pyrochlore, a characteristic shift in the Bi4f and Nb3d spectra to the region of lower energies by 0.15 and 0.60 eV, respectively, is observed. According to the XPS Cu2p and Mn2p spectra of pyrochlore, copper, and manganese cations are in a mixed charge state; they mainly have an effective charge of +2/+3, and the Cr2p spectrum is a superposition of the spectra of chromium ions in the charge state of +3, +4, +6. At 24 °С, the permittivity of the sample in the frequency range (104–106 Hz) weakly depends on the frequency and is equal to ~100, the dielectric loss tangent is 0.017. The activation energy of conductivity is equal to 0.41 eV. The specific electrical conductivity of Bi1.57Cr1/3Cu1/3Mn1/3Nb2O9−Δ increases with the temperature increasing from 1.8 × 10−5 Ohm−1·m−1 (24 °С) to 0.1 Ohm−1·m−1 (330 °С). Nyquist curves for the sample are modeled by equivalent electrical circuits. Full article
(This article belongs to the Section Chemistry Science)
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14 pages, 3547 KiB  
Article
Magnetic Metallic Nanoparticles Coated with Carbon for the Catalytic Removal of Bromate from Water
by Patrícia S. F. Ramalho, Olívia Salomé G. P. Soares, José J. M. Órfão and Manuel Fernando R. Pereira
Catalysts 2024, 14(2), 149; https://doi.org/10.3390/catal14020149 - 17 Feb 2024
Cited by 2 | Viewed by 1956
Abstract
Bromate, often detected in drinking water, is associated with a significant risk of cancer. Catalytic reduction has been recognized as an effective treatment technique to remove ions by reducing them over metal catalysts in the presence of a reducing agent, usually hydrogen. This [...] Read more.
Bromate, often detected in drinking water, is associated with a significant risk of cancer. Catalytic reduction has been recognized as an effective treatment technique to remove ions by reducing them over metal catalysts in the presence of a reducing agent, usually hydrogen. This work aims to synthesize metallic magnetic nanoparticles of iron oxide (FeO) and mixed iron oxides with manganese (MnFeO), cobalt (CoFeO), and copper (CuFeO) coated with carbon via chemical vapor deposition (C-MNP) to be applied as catalysts to the reduction of bromate in water. The use of magnetic nanoparticles coated with carbon enables catalyst recovery via magnetic separation and takes advantage of the catalytic properties of the carbon materials. The iron particles proved to be the most promising catalysts for the reduction of bromate into bromide, the highest removal being obtained with the CFeO@CVD750 sample, resulting in a 99% conversion after 120 min of reaction under the conditions tested. Due to its magnetic nature, the catalytic material was easily removed after the reaction and applied in four consecutive cycles without losing its catalytic properties. These results highlight the great potential of carbon-coated magnetic nanoparticles for reducing bromate in water. Full article
(This article belongs to the Section Environmental Catalysis)
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18 pages, 2250 KiB  
Review
Association between Heavy Metal Exposure and Parkinson’s Disease: A Review of the Mechanisms Related to Oxidative Stress
by Sarita Pyatha, Haesoo Kim, Daeun Lee and Kisok Kim
Antioxidants 2022, 11(12), 2467; https://doi.org/10.3390/antiox11122467 - 15 Dec 2022
Cited by 73 | Viewed by 9456
Abstract
Parkinson’s disease (PD) is a gradually progressing neurodegenerative condition that is marked by a loss of motor coordination along with non-motor features. Although the precise cause of PD has not been determined, the disease condition is mostly associated with the exposure to environmental [...] Read more.
Parkinson’s disease (PD) is a gradually progressing neurodegenerative condition that is marked by a loss of motor coordination along with non-motor features. Although the precise cause of PD has not been determined, the disease condition is mostly associated with the exposure to environmental toxins, such as metals, and their abnormal accumulation in the brain. Heavy metals, such as iron (Fe), mercury (Hg), manganese (Mn), copper (Cu), and lead (Pb), have been linked to PD and contribute to its progression. In addition, the interactions among the components of a metal mixture may result in synergistic toxicity. Numerous epidemiological studies have demonstrated a connection between PD and either single or mixed exposure to these heavy metals, which increase the prevalence of PD. Chronic exposure to heavy metals is related to the activation of proinflammatory cytokines resulting in neuronal loss through neuroinflammation. Similarly, metals disrupt redox homeostasis while inducing free radical production and decreasing antioxidant levels in the substantia nigra. Furthermore, these metals alter molecular processes and result in oxidative stress, DNA damage, mitochondrial dysfunction, and apoptosis, which can potentially trigger dopaminergic neurodegenerative disorders. This review focuses on the roles of Hg, Pb, Mn, Cu, and Fe in the development and progression of PD. Moreover, it explores the plausible roles of heavy metals in neurodegenerative mechanisms that facilitate the development of PD. A better understanding of the mechanisms underlying metal toxicities will enable the establishment of novel therapeutic approaches to prevent or cure PD. Full article
(This article belongs to the Special Issue Oxidative Stress-Induced Neurotoxicity and Mitochondrial Dysfunction)
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18 pages, 2275 KiB  
Review
Heterogeneous Metal-Activated Persulfate and Electrochemically Activated Persulfate: A Review
by Junjing Li, Yiqi Liang, Pengliang Jin, Bin Zhao, Zhaohui Zhang, Xiaojia He, Zilin Tan, Liang Wang and Xiuwen Cheng
Catalysts 2022, 12(9), 1024; https://doi.org/10.3390/catal12091024 - 9 Sep 2022
Cited by 39 | Viewed by 5571
Abstract
The problem of organic pollution in wastewater is an important challenge due to its negative impact on the aquatic environment and human health. This review provides an outline of the research status for a sulfate-based advanced oxidation process in the removal of organic [...] Read more.
The problem of organic pollution in wastewater is an important challenge due to its negative impact on the aquatic environment and human health. This review provides an outline of the research status for a sulfate-based advanced oxidation process in the removal of organic pollutants from water. The progress for metal catalyst activation and electrochemical activation is summarized including the use of catalyst-activated peroxymonosulfate (PMS) and peroxydisulfate (PDS) to generate hydroxyl radicals and sulfate radicals to degrade pollutants in water. This review covers mainly single metal (e.g., cobalt, copper, iron and manganese) and mixed metal catalyst activation as well as electrochemical activation in recent years. The leaching of metal ions in transition metal catalysts, the application of mixed metals, and the combination with the electrochemical process are summarized. The research and development process of the electrochemical activation process for the degradation of the main pollutants is also described in detail. Full article
(This article belongs to the Special Issue Advanced Catalytic Material for Water Treatment)
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26 pages, 11330 KiB  
Article
Distinguishing Genuine Imperial Qing Dynasty Porcelain from Ancient Replicas by On-Site Non-Invasive XRF and Raman Spectroscopy
by Philippe Colomban, Michele Gironda, Gulsu Simsek Franci and Pauline d’Abrigeon
Materials 2022, 15(16), 5747; https://doi.org/10.3390/ma15165747 - 20 Aug 2022
Cited by 18 | Viewed by 4364
Abstract
The combined use of non-invasive on-site portable techniques, Raman microscopy, and X-ray fluorescence spectroscopy on seven imperial bowls and two decorated dishes, attributed to the reigns of the Kangxi, Yongzheng, Qianlong, and Daoguang emperors (Qing Dynasty), allows the identification of the coloring agents/opacifiers [...] Read more.
The combined use of non-invasive on-site portable techniques, Raman microscopy, and X-ray fluorescence spectroscopy on seven imperial bowls and two decorated dishes, attributed to the reigns of the Kangxi, Yongzheng, Qianlong, and Daoguang emperors (Qing Dynasty), allows the identification of the coloring agents/opacifiers and composition types of the glazes and painted enamels. Particular attention is paid to the analysis of the elements used in the (blue) marks and those found in the blue, yellow, red, and honey/gilded backgrounds on which, or in reserve, a floral motif is principally drawn. The honey-colored background is made with gold nanoparticles associated with a lead- and arsenic-based flux. One of the red backgrounds is also based on gold nanoparticles, the second containing copper nanoparticles, both in lead-based silicate enamels like the blue and yellow backgrounds. Tin and arsenic are observed, but cassiterite (SnO2) is clearly observed in one of the painted decors (dish) and in A676 yellow, whereas lead (calcium/potassium) arsenate is identified in most of the enamels. Yellow color is achieved with Pb-Sn-Sb pyrochlore (Naples yellow) with various Sb contents, although green color is mainly based on lead-tin oxide mixed with blue enamel. The technical solutions appear very different from one object to another, which leads one to think that each bowl is really a unique object and not an item produced in small series. The visual examination of some marks shows that they were made in overglaze (A608, A616, A630, A672). It is obvious that different types of cobalt sources were used for the imprinting of the marks: cobalt rich in manganese for bowl A615 (Yongzheng reign), cobalt rich in arsenic for bowl A613 (but not the blue mark), cobalt with copper (A616), and cobalt rich in arsenic and copper (A672). Thus, we have a variety of cobalt sources/mixtures. The high purity of cobalt used for A677 bowl indicates a production after ~1830–1850. Full article
(This article belongs to the Special Issue Advanced Materials & Methods for Heritage & Archaeology)
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10 pages, 4005 KiB  
Article
Oxidative Synthesis of Acid Blue 7 Dye Catalyzed by CuO/Silicotungstic Acid in Water-Phase
by Akihiro Nomoto, Tomoya Okada, Yuki Yamamoto, Shota Kuroda, Kuniaki Marui, Mika Yamamoto, Hidetaka Tsujimoto, Michio Ueshima, Tamotsu Nishigahana, Keiji Itoh, Gohei Kobata, Shintaro Kodama and Akiya Ogawa
Materials 2021, 14(16), 4505; https://doi.org/10.3390/ma14164505 - 11 Aug 2021
Cited by 3 | Viewed by 3296
Abstract
A catalytic oxidation reaction for Acid Blue 7 dye synthesis was evaluated in water. Without lead oxide or manganese oxide derivatives as oxidants, polyoxometalate catalysts were investigated to reduce the usage of harmful heavy metal. A catalyst was prepared by mixing silicotungstic acid [...] Read more.
A catalytic oxidation reaction for Acid Blue 7 dye synthesis was evaluated in water. Without lead oxide or manganese oxide derivatives as oxidants, polyoxometalate catalysts were investigated to reduce the usage of harmful heavy metal. A catalyst was prepared by mixing silicotungstic acid with copper oxide, and aqueous hydrogen peroxide (30%) was used as an oxidizing agent. This reaction proceeded to produce Acid Blue 7 from the corresponding leuco acid after 45 min at 95 °C and was viable for a 10 g-scale synthesis. Full article
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8 pages, 1103 KiB  
Proceeding Paper
Leaching Kinetics of Selenium, Tellurium and Silver from Copper Anode Slime by Sulfuric Acid Leaching in the Presence of Manganese(IV) Oxide and Graphite
by Kurniawan Kurniawan, Jae-chun Lee, Jonghyun Kim, Rina Kim and Sookyung Kim
Mater. Proc. 2021, 3(1), 16; https://doi.org/10.3390/IEC2M-09233 - 6 Feb 2021
Cited by 2 | Viewed by 2226
Abstract
Sulfuric acid leaching of copper anode slime (CAS) in the presence of manganese(IV) oxide (MnO2) and graphite was investigated for Se, Te and Ag recovery. The study reveals that the leaching of Se, Te and Ag was facilitated by the galvanic [...] Read more.
Sulfuric acid leaching of copper anode slime (CAS) in the presence of manganese(IV) oxide (MnO2) and graphite was investigated for Se, Te and Ag recovery. The study reveals that the leaching of Se, Te and Ag was facilitated by the galvanic interaction with MnO2, and graphite played the role of a catalyst. The leaching process could yield 81.9% Se, 90.8% Te, and 80.7% Ag leaching efficiency when the conditions were maintained as 500 rpm, 2.0 M H2SO4, 0.8/0.8/1 MnO2/graphite/CAS, and 90 °C temperature. The kinetic study showed that Se leaching followed the surface chemical reaction at all the tested temperature range (25–90 °C) with the activation energy of 27.7 kJ/mol. Te and Ag leaching at temperature 25–50 °C followed the mixed and surface chemical reaction models, respectively, and changed to fit the diffusion and mixed control models, respectively, in the temperature range 60–90 °C with the corresponding activation energy of 17.8 and 12.2 kJ/mol. Full article
(This article belongs to the Proceedings of The 1st International Electronic Conference on Metallurgy and Metals)
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27 pages, 7491 KiB  
Article
A Combined Pyro- and Hydrometallurgical Approach to Recycle Pyrolyzed Lithium-Ion Battery Black Mass Part 1: Production of Lithium Concentrates in an Electric Arc Furnace
by Marcus Sommerfeld, Claudia Vonderstein, Christian Dertmann, Jakub Klimko, Dušan Oráč, Andrea Miškufová, Tomáš Havlík and Bernd Friedrich
Metals 2020, 10(8), 1069; https://doi.org/10.3390/met10081069 - 7 Aug 2020
Cited by 62 | Viewed by 15326
Abstract
Due to the increasing demand for battery raw materials such as cobalt, nickel, manganese, and lithium, the extraction of these metals not only from primary, but also from secondary sources like spent lithium-ion batteries (LIBs) is becoming increasingly important. One possible approach for [...] Read more.
Due to the increasing demand for battery raw materials such as cobalt, nickel, manganese, and lithium, the extraction of these metals not only from primary, but also from secondary sources like spent lithium-ion batteries (LIBs) is becoming increasingly important. One possible approach for an optimized recovery of valuable metals from spent LIBs is a combined pyro- and hydrometallurgical process. According to the pyrometallurgical process route, in this paper, a suitable slag design for the generation of slag enriched by lithium and mixed cobalt, nickel, and copper alloy as intermediate products in a laboratory electric arc furnace was investigated. Smelting experiments were carried out using pyrolyzed pelletized black mass, copper(II) oxide, and different quartz additions as a flux to investigate the influence on lithium-slagging. With the proposed smelting operation, lithium could be enriched with a maximum yield of 82.4% in the slag, whereas the yield for cobalt, nickel, and copper in the metal alloy was 81.6%, 93.3%, and 90.7% respectively. The slag obtained from the melting process is investigated by chemical and mineralogical characterization techniques. Hydrometallurgical treatment to recover lithium is carried out with the slag and presented in part 2. Full article
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18 pages, 5351 KiB  
Article
Promotional Effect of Gold on the WGS Activity of Alumina-Supported Copper-Manganese Mixed Oxides
by Tatyana Tabakova, Ivan Ivanov, Yordanka Karakirova, Daniela Karashanova, Anna Maria Venezia, Petya Petrova, Georgi Avdeev, Elitsa Kolentsova and Krasimir Ivanov
Catalysts 2018, 8(11), 563; https://doi.org/10.3390/catal8110563 - 20 Nov 2018
Cited by 12 | Viewed by 4038
Abstract
The water-gas shift (WGS) reaction is a well-known industrial process used for the production of hydrogen. During the last few decades, it has attracted renewed attention due to the need for high-purity hydrogen for fuel-cell processing systems. The aim of the present study [...] Read more.
The water-gas shift (WGS) reaction is a well-known industrial process used for the production of hydrogen. During the last few decades, it has attracted renewed attention due to the need for high-purity hydrogen for fuel-cell processing systems. The aim of the present study was to develop a cost-effective and catalytically efficient formulation that combined the advantageous properties of transition metal oxides and gold nanoparticles. Alumina-supported copper- manganese mixed oxides were prepared by wet impregnation. The deposition-precipitation method was used for the synthesis of gold catalysts. The effect of the Cu:Mn molar ratio and the role of Au addition on the WGS reaction’s performance was evaluated. Considerable emphasis was put on the characterization of the as-prepared and WGS-tested samples by means of a number of physicochemical methods (X-ray powder diffraction, high-resolution transmission electron microscopy, electron paramagnetic resonance, X-ray photoelectron spectroscopy, and temperature-programmed reduction) in order to explain the relationship between the structure and the reductive and WGS behavior. Catalytic tests revealed the promotional effect of gold addition. The best performance of the gold-promoted sample with a higher Cu content, i.e., a Cu:Mn molar ratio of 2:1 might be related to the beneficial role of Au on the spinel decomposition and the highly dispersed copper particle formation during the reaction, thus, ensuring the presence of two highly dispersed active metallic phases. High-surface-area alumina that was modified with a surface fraction of Cu–Mn mixed oxides favored the stabilization of finely dispersed gold particles. These new catalytic systems are very promising for practical applications due to their economic viability because the composition mainly includes alumina (80%). Full article
(This article belongs to the Special Issue Catalysts for Water-Gas Shift Reaction)
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16 pages, 3344 KiB  
Article
Anodic Lodes and Scrapings as a Source of Electrolytic Manganese
by Daniel Fernández-González, José Sancho-Gorostiaga, Juan Piñuela-Noval and Luis Felipe Verdeja González
Metals 2018, 8(3), 162; https://doi.org/10.3390/met8030162 - 7 Mar 2018
Cited by 7 | Viewed by 4386
Abstract
Manganese is an element of interest in metallurgy, especially in ironmaking and steel making, but also in copper and aluminum industries. The depletion of manganese high grade sources and the environmental awareness have led to search for new manganese sources, such as wastes/by-products [...] Read more.
Manganese is an element of interest in metallurgy, especially in ironmaking and steel making, but also in copper and aluminum industries. The depletion of manganese high grade sources and the environmental awareness have led to search for new manganese sources, such as wastes/by-products of other metallurgies. In this way, we propose the recovery of manganese from anodic lodes and scrapings of the zinc electrolysis process because of their high Mn content (>30%). The proposed process is based on a mixed leaching: a lixiviation-neutralization at low temperature (50 °C, reached due to the exothermic reactions involved in the process) and a lixiviation with sulfuric acid at high temperature (150–200 °C, in heated reactor). The obtained solution after the combined process is mainly composed by manganese sulphate. This solution is then neutralized with CaO (or manganese carbonate) as a first purification stage, removing H2SO4 and those impurities that are easily removable by controlling pH. Then, the purification of nobler elements than manganese is performed by their precipitation as sulphides. The purified solution is sent to electrolysis where electrolytic manganese is obtained (99.9% Mn). The versatility of the proposed process allows for obtaining electrolytic manganese, oxide of manganese (IV), oxide of manganese (II), or manganese sulphate. Full article
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