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13 protocols using mn2o3

1

Synthesis and Characterization of NaCu0.2Fe0.3Mn0.5O2

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The NaCu0.2Fe0.3Mn0.5O2 compound was synthesized using a solid-state reaction. The precursors, of Na2CO3 (99%), CuO (99%), Fe2O3 (99%) and Mn2O3 (99%) were obtained from Sigma-Aldrich, and were mixed in proportional ratios. The obtained powder was burned at 500 °C for 16 h, and then, the sample was ground, pressed into pellets and transferred to an oven at 850 °C for 24 h.
To determine the purity of the sample, powder XRD was performed using a Bruker D8 Discover with Twin/Twin optics, at room temperature, with Cu Kα radiation (λ = 1.5406 Å, 10° ≤ 2θ ≤ 80°). To precisely determine the optical properties of the prepared sample, a Shimadzu UV-3101 PC scanning spectrophotometer was used at room temperature, with a wavelength range of 200–800 nm, with a sample pellet of 0.5 mm of diameter. Finally, the electrical property measurements were obtained using complex impedance spectroscopy with a Solartron SI 1260 impedance/gain phase analyzer in the temperature and frequency ranges of 333–453 K and 10−1 to 106 Hz, respectively, with a sample pellet with a thickness of 1 mm and a diameter of 8 mm.
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2

Catalytic Transformation of Glass Beads

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Commercial 2.0 mm borosilicate glass bead (Sigma Aldrich) was utilized as a support under DBD plasma condition. Then, various metal oxides were loaded on the spherical glass bead. The catalyst was prepared by following procedure32 (link). The glass beads were etched with 5 M NaOH (≥98%, Sigma Aldrich) solution at 100 °C, followed by immersing it in a suspension of metal oxide. Next, the mixture was dried at 19 120 °C for 1 h and washed with distilled water. The operation was repeated several times until the glass beads were no longer transparent with desired content of metal oxide. MnO (99%, Sigma Aldrich), Mn2O3 (99.9%, Sigma Aldrich), MnO2 (≥99%, Sigma Aldrich), Fe2O3 (≥99%, Sigma Aldrich), NiO (99%, Sigma Aldrich), and Co3O4 (99.5%, Sigma Aldrich) were used as metal oxides. Fixed amount (1 wt%) of metal oxides were loaded to each of the catalysts. 4.0 g of catalysts were used in the reaction. X-Ray Diffraction (RIGAKU SMARTLAB) with a Cu Kα radiation operated at 40 kV and 50 mA was utilized to verify the solid-state phases of the catalysts. In addition, the N2 adsorption/desorption method by an ASAP 2010 instrument (Micromeritics Co.) was employed in order to obtain the specific surface area of the catalysts.
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3

Synthesis of P2-type Sodium Iron Manganese Oxides

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P2-type
sodium iron manganese
oxides—Na0.67Fe0.5Mn0.5O2, Na0.67Fe0.50Mn0.45Ti0.05O2, Na0.67Fe0.50Mn0.40Ti0.10O2, Na0.67Fe0.45Mn0.50Ti0.05O2, and Na0.67Fe0.40Mn0.50xTi0.10O2—were synthesized by a solid-state
reaction and are denoted as NFMO, Mn–Ti05, Mn–Ti10,
Fe–Ti05, and Fe–Ti10, respectively. Na2CO3 (Samchun), Fe2O3 (Samchun), Mn2O3 (Sigma-Aldrich), and TiO2 (Daejung)
were homogeneously mixed together and precalcined at 450 °C for
6 h in air. Then, the precalcined material was pelletized, and the
pellet was calcined at 900 °C for 15 h in air.
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4

Electrochemical Synthesis of Metal Oxides

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Co(NO3)2 ⋅6H2O (≥99.999 %), Co3O4 (99.99), CoO (99.99 %), LiCoO2 (>99.8 %), Mn(NO3)2 ⋅4H2O (≥99.99 %), Mn(SO4)2⋅xH2O (99.99), MnO2 (≥99 %), Mn3O4 (≥97 %), Mn2O3 (≥99.9 %), L‐(+)‐Tartaric acid (≥99.5 %) and (2 M and 0.1 M) NaOH solutions were ordered from Sigma‐Aldrich. Graphite foil (≥99.8) with a thickness of 0.254 mm ordered from VWR. All reactants were used as received, without any further treatment. Solutions were prepared with deionized water (>18 MΩ cm).
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5

Synthesis of Manganese and Nickel Oxides

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Mn(CH3COO)3-2H2O (99%), Ni(CH3COO)2-4H2O (99%), 1-octadecene (90%), myristic acid (99%), decanol (98%), MnO (99.99%), Mn3O4 (97%), Mn2O3 (99.9%), NaH2PO4-H2O (99.0%, ACS reagent), and Na2HPO4-7H2O (98.0–102.0%, ACS reagent) were purchased from Sigma Aldrich. Ni(NO3)2–6H2O (99.9985%), MnO2 (99.9%), and Pt foil (99.997%) were purchased from Alfa Aesar. Acetone (99.5%), toluene (99.5%), hexane (95%), cyclohexane (99.5%), and ethanol (99.5%) were purchased from Daejung Chemicals. All chemicals used as received without further purification. Fluorine doped tin oxide coated glass (FTO) with the surface resistivity of 8 Ω sq–1 was obtained as 1.0 cm × 1.5 cm pre-cut glass pieces.
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6

Manganese Oxide Synthesis and Characterization

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All chemicals (H2SO4, H2O2, Mn(CH3COO)2·4H2O, polyethylene oxide (PEO, MW = 106), Na2SO4, NaH2PO4·2H2O and Na2HPO4·H2O) and commercial manganese oxides (Mn2O3, Mn3O4, and activated porous MnO2) were purchased from Sigma-Aldrich (Munich, Germany).
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7

Synthesis of Mixed Manganese-Ruthenium Oxides

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Synthesis of mixed manganese-ruthenium oxides was based on the hydrothermal route of DeGuzman et al. who prepared manganese oxides, 20 but with the addition of KRuO 4 as oxidant, as well as KMnO 4 , to oxidise Mn 2+ . A solution of 0.2945 g (0.001864 moles) KMnO 4 in 5 mL of water, was added to a solution of 0.44 g (0.0026 moles) MnSO 4 •H 2 O in 1.5 mL of water and 0.7112 g concentrated H 2 SO 4 was added to give a final concentration of 1 mol dm -3 H 2 SO 4 . Varying amounts of KRuO 4 were substituted for the KMnO 4 (as described in the Results and Discussion section). The mixtures were then heated in 20 ml Teflon-lined Parr autoclaves, at a temperature of either 100 °C or 200 °C, for 24 hours. The solid products were recovered by centrifuge, washed with deionised water and dried at 80 °C in air. All chemicals were used as provided by Sigma-Aldrich. For the XANES spectroscopy experiments, the reference materials Mn(NO 3 ) 2 , Mn 2 O 3 , Mn 3 O 4 , MnO 2 , Ru(acac) 3 were also purchased from Sigma-Aldrich at the highest available purity and their identity confirmed using powder XRD, while the material La 4.87 Ru 2 O 12 was synthesised as in our previous work. 19a
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8

Synthesis of P2-type Na-Li-Mn Oxide

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P2‐type Na0.6Li0.2Mn0.8O2 powder was synthesized through a solid‐state reaction with Na2CO3 (Kanto chemical), Li2CO3 (Alfa Aesar), and Mn2O3 (Sigma Aldrich) as the metallic precursors. Accurate stoichiometric amounts of the precursor powders, without excess Na or Li sources, were homogeneously mixed via ball milling with acetone. After drying at 65 °C for 2 h, the powder mixture was heat‐treated in air at 900 °C for 10 h and was naturally allowed to cool to room temperature. To avoid unfavorable side reactions with the ambient atmosphere and moisture, the synthesized powder was transferred to an argon‐filled glove box after the heat treatment.
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9

Air-Scrubbing for Na Extraction

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Air-scrubbing tests are performed using a small 4-in. closed-end Al2O3 tube with an outer diameter of 1 in. and an inner diameter of 0.75 in. A 60-sccm flowrate of air is supplied with a small 5VDC diaphragm pump with a potentiometer to control the flowrate. The same RGA as above is used to track CO2 concentration during Na extraction. A ppm level CO2 calibration is obtained for the RGA by diluting atmospheric air with nitrogen in various ratios. NaMnO2 used in tests was synthesized via solid-state synthesis using stoichiometric amounts of Mn2O3 (Sigma-Aldrich) and Na2CO3 heated in flowing air at 700 °C for 6 h.
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10

Characterization of Manganese Oxide Nanoparticles

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Particulate Mn2O3-NPs with a size of 30 nm, 99.2% purity, surface area of 150 m2 g-1, and true density of ~0.35 g-1 cm3 were obtained from NANOSANY Co. Ltd, Mashhad, Iran. Their physico-chemical properties, including scanning electron microscopy (SEM), transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) have been presented in Figure S1. MnSO4, MnCl2 and Mn2O3 were also purchased from Sigma Aldrich (Germany).
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