一氧化锰

一氧化锰是锰的一种氧化物，化学式MnO，在自然界中以罕见的方锰矿（英语：manganosite）的形式存在。^[2]它在磁共振成像、电极材料制备等方面有着潜在应用。^[3]

一氧化锰
IUPAC名 Manganese(II) oxide 氧化锰(II)
别名	氧化亚锰 C.I. 77726
识别
CAS号	1344-43-0  Y
PubChem	14940
RTECS	OP0900000
性质
化学式	MnO
摩尔质量	70.9374 g·mol⁻¹
外观	绿色晶体
密度	5.37 g/cm3 (23 °C)
熔点	1785 °C[1]
溶解性（水）	不溶
折光度n D	2.16
结构
晶体结构	石盐 (立方晶系), cF8
空间群	Fm3m, No. 225
配位几何	八面体 (Mn2+) 八面体 (O2–)
危险性
欧盟编号	未列出
闪点	不可燃
相关物质
其他阴离子	硫化锰 硒化锰 碲化锰
其他阳离子	一氧化铬 氧化亚铁
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

结构

一氧化锰有着与氯化钠晶体相同的结构，其阴、阳离子都处于八面体的配位环境中，它有着非化学计量比的组成，可由MnO变化到MnO_1.045^[4]。在118 K以下时，一氧化锰具有反铁磁性^[4]，其磁结构（英语：magnetic structure）最初于1951年由中子衍射得到表征。^[5]。其禁带宽度为4.02 eV，自旋磁矩为4.52 μ_B。^[6]

制备

一氧化锰可由氢气还原锰的高价氧化物得到^[4]，如：

${\displaystyle \mathrm {MnO} _{2}+\mathrm {H} _{2}\longrightarrow \mathrm {MnO} +\mathrm {H} _{2}\mathrm {O} }$

工业上用氢气、一氧化碳或甲烷还原二氧化锰制得：^[2]

${\displaystyle \mathrm {MnO} _{2}+\mathrm {CO} \longrightarrow \mathrm {MnO} +\mathrm {CO} _{2}}$

一氧化锰也可由碳酸锰的热分解制得：^[7]

${\displaystyle \mathrm {MnCO} _{3}\longrightarrow \mathrm {MnO} +\mathrm {CO} _{2}}$

草酸锰的热分解根据产物的不同会生成一氧化锰、α-三氧化二锰或四氧化三锰，其中在真空中于500 °C分解可以得到一氧化锰。^[8]

化学性质

一氧化锰和30%盐酸反应，放出大量热，使反应液沸腾。

一氧化锰不溶于水^[2]，是一种离子型的碱性氧化物，和酸反应得到相应的二价锰盐。^[4]例如：^[9]

${\displaystyle \mathrm {CF} _{3}\mathrm {SO} _{3}\mathrm {H} +\mathrm {MnO} \longrightarrow \mathrm {(CF} _{3}\mathrm {SO} _{3}\mathrm {)} _{2}\mathrm {Mn+} \mathrm {H} _{2}\mathrm {O} }$

它在高温下和氢氧化钠反应，生成锰(III)酸钠并放出氢气：^[10]

${\displaystyle \mathrm {2MnO} +\mathrm {2NaOH} \longrightarrow \mathrm {NaMnO} _{2}+\mathrm {H} _{2}\uparrow }$

它和氯化铁反应得到铁酸锰：^[11]

${\displaystyle \mathrm {2FeCl} _{3}+\mathrm {4MnO} \longrightarrow \mathrm {MnFe} _{2}\mathrm {O} _{4}+\mathrm {3MnCl} _{2}}$

它和氧化钡、锰(III)酸钇于高温反应，可以得到具有层状钙钛矿结构的化合物YBaMn₂O₅；^[12]和五氧化二钒或偏钒酸铵反应，得到具有钪钇石（英语：Thortveitite）结构的Mn₂V₂O₇。^[13] 它可以直接用作反应物来构建其它一些含锰材料，如(H₂dmp)_0.5Mn(H₂PO₄)(C₂O₄)^[14]、Na₃Mn₂SbO₆等。^[15]

参考文献

1. Hay, R.; Howat, D. D.; White, James. Slag systems. Journal of the West of Scotland Iron and Steel Institute, 1934. 41: 97-105. ISSN: 0083-825X.
2. Pradyot Patnaik (2002) Handbook of Inorganic Chemicals, McGraw-Hill Professional, ISBN 0070494398
3. 王涛, 周菊红. 一氧化锰纳米材料的研究进展. 广州化工, 2016, 44(21):10-12. doi:10.3969/j.issn.1001-9677.2016.21.005
4. Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
5. Shull, C. G.; Strauser, W. A.; Wollan, E. O. Neutron Diffraction by Paramagnetic and Antiferromagnetic Substances. Physical Review. 1951, 83 (2): 333–345. ISSN 0031-899X. doi:10.1103/PhysRev.83.333.
6. Franchini, C.; Bayer, V.; Podloucky, R.; Paier, J.; Kresse, G. Density functional theory study of MnO by a hybrid functional approach. Physical Review B. 2005, 72 (4). ISSN 1098-0121. doi:10.1103/PhysRevB.72.045132.
7. W.H. McCarroll (1994) Oxides- solid sate chemistry, Encyclopedia of Inorganic chemistry Ed. R. Bruce King, John Wiley & Sons ISBN 0-471-93620-0
8. Ahmad, Tokeer; Ramanujachary, Kandalam V.; Lofland, Samuel E.; Ganguli, Ashok K. Nanorods of manganese oxalate: a single source precursor to different manganese oxide nanoparticles (MnO, Mn2O3, Mn3O4). Journal of Materials Chemistry. 2004, 14 (23): 3406. ISSN 0959-9428. doi:10.1039/b409010a.
9. Sniekers, Jeroen; Malaquias, João C.; Van Meervelt, Luc; Fransaer, Jan; Binnemans, Koen. Manganese-containing ionic liquids: synthesis, crystal structures and electrodeposition of manganese films and nanoparticles. Dalton Transactions. 2017, 46 (8): 2497–2509. ISSN 1477-9226. doi:10.1039/C6DT04781E.
10. Kreider, Peter B.; Funke, Hans H.; Cuche, Kevin; Schmidt, Michael; Steinfeld, Aldo; Weimer, Alan W. Manganese oxide based thermochemical hydrogen production cycle. International Journal of Hydrogen Energy. 2011, 36 (12): 7028–7037. ISSN 0360-3199. doi:10.1016/j.ijhydene.2011.03.003.
11. Muroi, M.; Street, R.; McCormick, P. G.; Amighian, J. Magnetic properties of ultrafineMnFe2O4powders prepared by mechanochemical processing. Physical Review B. 2001, 63 (18). ISSN 0163-1829. doi:10.1103/PhysRevB.63.184414.
12. Chapman, Jon P.; Attfield, J. Paul; Molgg, Michele; Friend, Chris M.; Beales, Tim P. A Ferrimagnetic Manganese Oxide with a Layered Perovskite Structure: YBaMn₂O₅. Angewandte Chemie International Edition in English. 1996, 35 (21): 2482–2484. ISSN 0570-0833. doi:10.1002/anie.199624821.
13. Knowles, Kevin M.; Sil, Anjan; Stöger, Berthold; Weil, Matthias. Crystal structure of the thortveitite-related M phase, (Mn_xZn_1-x)₂V₂O₇ (0.75<x<0.913)： a combined synchrotron powder and single-crystal X-ray study. Acta Crystallographica Section C Structural Chemistry. 2018, 74 (10): 1079–1087. ISSN 2053-2296. doi:10.1107/S2053229618010458.
14. Luan, Lindong; Zou, Guohong; Lin, Zhien; Cai, Huaqiang; Huang, Hui. Solvent-free synthesis of metal phosphate-oxalates with layered and zeolitic structures. Inorganic Chemistry Communications. 2018, 96: 65–68. ISSN 1387-7003. doi:10.1016/j.inoche.2018.08.003.
15. Yadav, Dileep Kumar; Sethi, Aanchal; Shalu, Shalu; Uma, S. New series of honeycomb ordered oxides, Na₃M₂SbO₆ (M(II) = Mn, Fe, (Mn, Fe), (Mn, Co)): synthesis, structure and magnetic properties. Dalton Transactions. 2019, 48 (24): 8955–8965. ISSN 1477-9226. doi:10.1039/C9DT01194C.

拓展阅读

1. Spear, Frank S.; Cheney, John T. A petrogenetic grid for pelitic schists in the system SiO₂-Al₂O₃-FeO-MgO-K₂O-H₂O. Contributions to Mineralogy and Petrology. 1989, 101 (2): 149–164. ISSN 0010-7999. doi:10.1007/BF00375302.
2. Wu, Rongcheng; Qu, Jiuhui; Chen, Yongsheng. Magnetic powder MnO–Fe₂O₃ composite—a novel material for the removal of azo-dye from water. Water Research. 2005, 39 (4): 630–638. ISSN 0043-1354. doi:10.1016/j.watres.2004.11.005.
3. Dong, Shun; Tang, Weikang; Hu, Peitao; Zhao, Xiaoguang; Zhang, Xinghong; Han, Jiecai; Hu, Ping. Achieving Excellent Electromagnetic Wave Absorption Capabilities by Construction of MnO Nanorods on Porous Carbon Composites Derived from Natural Wood via a Simple Route. ACS Sustainable Chemistry & Engineering. 2019, 7 (13): 11795–11805. ISSN 2168-0485. doi:10.1021/acssuschemeng.9b02100.