一氧化錳

一氧化錳
	IUPAC名; Manganese(II) oxide; 氧化錳(II)
別名	氧化亞錳; C.I. 77726
識別
CAS號	1344-43-0
PubChem	14940
RTECS	OP0900000
性質
化學式	MnO
摩爾質量	70.9374 g·mol⁻¹
外觀	綠色晶體
密度	5.37 g/cm3 (23 °C)
熔點	1785 °C
溶解性（水）	不溶
折光度n; D	2.16
結構
晶體結構	石鹽 (立方晶系), cF8
空間群	Fm3m, No. 225
配位幾何	八面體 (Mn2+); 八面體 (O2–)
危險性
歐盟編號	未列出
閃點	不可燃
相關物質
其他陰離子	硫化錳; 硒化錳; 碲化錳
其他陽離子	一氧化鉻; 氧化亞鐵
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

一氧化錳是錳的一種氧化物，化學式MnO，在自然界中以罕見的方錳礦（英語：manganosite）的形式存在。^[2]它在磁共振成像、電極材料製備等方面有着潛在應用。^[3]

結構

一氧化錳有着與氯化鈉晶體相同的結構，其陰、陽離子都處於八面體的配位環境中，它有着非化學計量比的組成，可由MnO變化到MnO_1.045^[4]。在118 K以下時，一氧化錳具有反鐵磁性^[4]，其磁結構（英語：magnetic structure）最初於1951年由中子繞射得到表徵。^[5]。其禁帶寬度為4.02 eV，自旋磁矩為4.52 μ_B。^[6]

製備

一氧化錳可由氫氣還原錳的高價氧化物得到^[4]，如：

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

工業上用氫氣、一氧化碳或甲烷還原二氧化錳製得：^[2]

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

一氧化錳也可由碳酸錳的熱分解製得：^[7]

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

草酸錳的熱分解根據產物的不同會生成一氧化錳、α-三氧化二錳或四氧化三錳，其中在真空中於500 °C分解可以得到一氧化錳。^[8]

化學性質

一氧化錳和30%鹽酸反應，放出大量熱，使反應液沸騰。

一氧化錳不溶於水^[2]，是一種離子型的鹼性氧化物，和酸反應得到相應的二價錳鹽。^[4]例如：^[9]

\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}

它在高溫下和氫氧化鈉反應，生成錳(III)酸鈉並放出氫氣：^[10]

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

它和氯化鐵反應得到鐵酸錳：^[11]

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

它和氧化鋇、錳(III)酸釔於高溫反應，可以得到具有層狀鈣鈦礦結構的化合物YBaMn₂O₅；^[12]和五氧化二釩或偏釩酸銨反應，得到具有鈧釔石（英語：Thortveitite）結構的Mn₂V₂O₇。^[13] 它可以直接用作反應物來構建其它一些含錳材料，如(H₂dmp)_0.5Mn(H₂PO₄)(C₂O₄)^[14]、Na₃Mn₂SbO₆等。^[15]

參考文獻

^ 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.
^ ^2.0 ^2.1 ^2.2 Pradyot Patnaik (2002) Handbook of Inorganic Chemicals, McGraw-Hill Professional, ISBN 0070494398
^ 王濤, 周菊紅. 一氧化錳納米材料的研究進展. 廣州化工, 2016, 44(21):10-12. doi:10.3969/j.issn.1001-9677.2016.21.005
^ ^4.0 ^4.1 ^4.2 ^4.3 Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
^ 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.
^ 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.
^ W.H. McCarroll (1994) Oxides- solid sate chemistry, Encyclopedia of Inorganic chemistry Ed. R. Bruce King, John Wiley & Sons ISBN 0-471-93620-0
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.
^ 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.

拓展閱讀

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.
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.
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.

[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.

[Patnaik-2] 2.0 ^2.1 ^2.2 Pradyot Patnaik (2002) Handbook of Inorganic Chemicals, McGraw-Hill Professional, ISBN 0070494398

[3] 王濤, 周菊紅. 一氧化錳納米材料的研究進展. 廣州化工, 2016, 44(21):10-12. doi:10.3969/j.issn.1001-9677.2016.21.005

[Greenwood-4] 4.0 ^4.1 ^4.2 ^4.3 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.

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