铕化合物

铕化合物是镧系金属铕（元素符号：Eu）形成的化合物，在这些化合物中，铕一般显+3价，如EuCl₃、Eu(NO₃)₃等；+2价的铕化合物是已知的，这也是水溶液中镧系金属最稳定的二价离子。^[1]

铕化合物在395 nm和365 nm的紫外光下发出荧光。

硝酸铕和氢氧化钠反应，生成氢氧化铕沉淀。反应用365 nm的紫外光照射。

氧族化物

氧化亚铕（俄语：Оксид европия(II)）可由氧化铕在高温下用金属铕还原得到，它具有岩盐结构，为深红色固体，在77 K具有铁磁性。它有成为磁制冷（英语：Magnetic refrigeration）材料的潜力（ΔS_mag=−143 mg/cm³ K，50 kOe）。^[2]^[3]硫化亚铕也具有铁磁性，但碲化亚铕却是反铁磁性的。^[2]铕的混合价态氧化物Eu₃O₄可由氧化铕用还原剂在氢气气氛下还原得到，如：^[4]

2 Eu₂O₃ + 2 EuOCl + 2 LiH → 2 Eu₃O₄ + 2 LiCl + H₂↑

三氧化二铕（氧化铕）是铕最稳定的氧化物，是高熔点的浅粉色固体，可由硝酸铕的热分解反应制得。^[2]它和水反应，可以得到EuOOH。^[5]可溶性铕盐和氨水或氢氧化钠反应，能够沉淀出氢氧化物Eu(OH)₃，但有多羟基化合物（如葡萄糖）存在时，沉淀不完全。^[2]三硫化二铕可由Eu(Et₂NCS₂)₃·Phen在500~600 °C分解制得，^[6]硫氰酸盐Eu(NCS)₃的分解也会得到三硫化二铕；^[7]它的两种晶型α型和γ型分别属正交晶系和立方晶系。^[8] 氧硫化铕由氧化铕在二硫化碳/氩/低压氧气流中反应得到，它是三斜晶系的固体，空间群P3m1，其光学带隙为4.4 eV。^[9]氧硒化铕和氧碲化铕可以由氧化铕和硒或碲在600 °C反应制得，^[10]氧硒化物在空气中加热，氧化为氧亚硒酸盐，^[11]氧碲化物也会发生类似反应，得到Eu₂TeO₆。^[12]

金属铕在固态氩中和水反应，可以得到Eu(H₂O)和Eu(H₂O)₂配合物。Eu(H₂O)经过重排得到HEuOH，并进一步分解为EuO和H₂；Eu(H₂O)₂则分解为Eu(OH)₂和H₂。^[13]

卤化物

铕可以形成EuX₃（X=F, Cl, Br, I）四种卤化物，除氟化物外均易溶于水，在水中是强电解质。无水卤化铕可由氧化物或卤化物的水合物反应制得：^[14]

Eu₂O₃ + 6 NH₄Cl → 2 EuCl₃ + 3 H₂O + 6 NH₃↑

EuCl₃·6H₂O + 6 SOCl₂ → EuCl₃ + 6 SO₂↑ + 12 HCl↑

其中，碘化铕只能通过氧化铕和氢碘酸反应得到^[15]，直接用碘化铵处理反应物会得到二价的碘化亚铕。^[16]

含氧酸盐

硫酸亚铕是二价铕的硫酸盐，它可由汞作为阴极，电解硫酸铕的溶液得到，或者用锌汞齐还原氯化铕，再和硫酸反应制得。^[17]它和碳酸钠或草酸铵反应，可以分别得到碳酸亚铕和草酸亚铕。^[17]

EuSO₄ + Na₂CO₃ + xH₂O → EuCO₃·xH₂O + Na₂SO₄

EuSO₄ + (NH₄)₂C₂O₄(饱和) + H₂O → EuC₂O₄·H₂O + (NH₄)₂SO₄

三价的硫酸铕可以直接由氧化铕和稀硫酸反应，并结晶得到，对水合物的脱水可以得到无水物。硫酸铕可溶于水，其八水合物在20 °C时的溶解度为2.56 g。^[18]铕的亚硫酸盐（Eu₂(SO₃)₃·nH₂O，n=0, 3, 6^[19]）及其碱式盐（EuOHSO₃·4H₂O^[20]）是已知的，亚硫酸盐在一氧化碳气氛中加热，会经过脱水得到无水物，经过Eu₂O₂SO₄，最终得到氧硫化物Eu₂O₂S。^[21]

硝酸铕可由氧化铕和硝酸反应并结晶得到，晶体用45~55%硫酸干燥，可以得到六水合物。^[22]其无水物可以通过氧化铕和四氧化二氮反应得到，而加热水合物只能得到碱式盐EuONO₃。^[23]磷酸铕可以通过氯化铕和磷酸氢二铵（或氧化铕和5 mol/L的磷酸^[24]）反应得到，其白色的一水合物从溶液中沉淀。它在600~800 °C失水，由一水的六方相转变为无水的单斜相。^[25]氧化铕和五氧化二砷反应，得到砷酸铕，它是无色晶体，具有磷钇矿结构。^[26]

碳酸铕是铕的碳酸盐之一，可由二氧化碳饱和的碳酸氢钠稀溶液与可溶性铕盐反应得到，它加热分解，生成氧化铕和二氧化碳。其碱式盐及复盐是已知的。^[27]乙酸铕是浅粉色的固体，可以从水溶液中结晶出四水合物，它用硫酸干燥得到三水合物。^[28]硝酸铕和草酸反应得到草酸铕十水合物，它在100 °C转化为五水合物。原料使用草酸钾只能得到复盐KEu(C₂O₄)₂·2H₂O。^[28]将草酸铕和草酸于200 °C进行草酸反应，可以得到配位聚合物[Eu(C₂O₄)(HCOO)]_n。^[29]草酸铕在二氧化碳气氛中加热至320 °C，可以得到草酸亚铕：^[30]

Eu₂(C₂O₄)₃ → 2 EuC₂O₄ + 2 CO₂↑

有机铕化合物

有机铕化合物是含Eu–C键的一类金属有机化合物，早期研究的有铕的环戊二烯配合物，它们可以由茂基钠和无水卤化铕在四氢呋喃中反应制得，如：^[32]^[33]

EuCl₃ + 3 C₅H₅Na → (C₅H₅)₃Eu + 3 NaCl

EuI₂ + 2 (C₅HⁱPr₄)Na → (C₅HⁱPr₄)₂Eu + 2 NaI

三茂铕是棕色固体，可以和过氧化氢反应得到环戊二烯过氧化铕^[34]；二(四异丙基茂)铕是橙红色固体，可于165 °C熔化。^[33]环壬四烯和铕(II)的配合物可以由类似方法制得，它的甲苯溶液在516 nm发出蓝绿色的荧光，相比其它有机铕(II)夹心配合物（约630 nm）有着明显的蓝移。^[35]

除了利用复分解反应制备有机铕化合物外，也能直接通过金属铕参与反应，如铕和五甲基环戊二烯反应生成浅橙色的二(五甲基环戊二烯)铕；^[33]和环辛四烯反应，得到浅绿色的环辛四烯铕。^[36]

应用

三价铕的化合物在激发下可以发出红光，如氧化铕可用于显像管电视中，^[37]掺铕氧硫化钇（Y₂O₂S:Eu³⁺）可用作荧光粉等。^[38]此外，铕化合物还能用于防伪材料制造。^[39]

参考文献

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参考书籍

易宪武, 黄春辉, 王慰, 刘余九, 吴瑾光. 无机化学丛书第七卷钪、稀土元素. 北京: 科学出版社, 1992. ISBN 9787030305749.
日本化学会编. 安家驹, 陈之川译. 无机化合物合成手册第二卷. 北京: 化学工业出版社, 1986. CSBN 15063·3726 （无机化合物の合成Ⅱ. 东京: 丸善株式会社, 1977）

[1] [1]
无机化学丛书. pp 187-188. 1.2.3 氧化态及电极电势.

[wucong-EuE-2] [2]
无机化学丛书. pp 200-203. 2. 氧族化合物; pp 215. 3. 氧化物及氢氧化物.

[3] [3]
Ahn, Kyunghan; Pecharsky, A. O.; Gschneidner, K. A.; Pecharsky, V. K. Preparation, heat capacity, magnetic properties, and the magnetocaloric effect of EuO. Journal of Applied Physics. 2005, 97 (6): 063901. ISSN 0021-8979. doi:10.1063/1.1841463.

[4] [4]
Georg Brauer (Hrsg.), unter Mitarbeit von Marianne Baudler u. a.: Handbuch der Präparativen Anorganischen Chemie. 3., umgearbeitete Auflage. Band I, Ferdinand Enke, Stuttgart 1975, pp 1091. ISBN 3-432-02328-6.

[5] [5]
Batsanov, S. S.; Deribas, A. A.; Kustova, G. N. Reaction of rare earth metal oxides with water. Zhurnal Neorganicheskoi Khimii, 1967. 12 (9): 2283-2286. ISSN 0044-457X.

[6] [6]
Kuzmina, N. P.; Ivanov, R. A.; Paramonov, S. E.; Martynenko, L. I. Volatile lanthanide diethyldithiocarbamates as precursors for lanthanide sulfide film deposition. Proceedings - Electrochemical Society, 1997. 97 (25). 880-885. ISSN: 0161-6374.

[7] [7]
Grizik, A. A.; Eliseev, A. A.; Borodulenko, G. P.; Tolstova, V. A. Low-temperature form of Ln2S3 (Ln = europium, samarium, or gadolinium). Zhurnal Neorganicheskoi Khimii, 1977. 22 (2): 558-559. ISSN: 0044-457X.

[8] [8]
Roméro, Stéphane; Mosset, Alain; Trombe, Jean-Christian; Macaudière, Pierre. Low-temperature process of the cubic lanthanide sesquisulfides:remarkable stabilization of the γ-Ce2S3 phasei. Journal of Materials Chemistry. 1997, 7 (8): 1541–1547. ISSN 0959-9428. doi:10.1039/a608443e.

[9] [9]
Llanos, J; Sánchez, V; Mujica, C; Buljan, A. Synthesis, physical and optical properties, and electronic structure of the rare-earth oxysulfides Ln₂O₂S (Ln=Sm, Eu). Materials Research Bulletin. 2002, 37 (14): 2285–2291. ISSN 0025-5408. doi:10.1016/S0025-5408(02)00936-4.

[10] [10]
Sadovskaya, O. A.; Yarembash, E. I.; Eliseev, A. A. Europium oxychalcogenides. Izvestiya Akademii Nauk SSSR, Neorganicheskie Materialy, 1974. 10 (11): 2076-2077. ISSN 0002-337X.

[11] [11]
Markku Leskela. Thermal stability and infrared absorption spectrum of europium oxyselenide (Eu₂O₂Se). Finnish Chemical Letters, 1980 (6): 173-176. ISSN 0303-4100.

[12] [12]
Kent, Richard A.; Eick, Harry A. The Preparation and Properties of Some Lanthanum(III) Monotelluroöxides. Inorganic Chemistry. 1962, 1 (4): 956–958. ISSN 0020-1669. doi:10.1021/ic50004a061.

[13] [13]
Jia Xu, Mingfei Zhou. Reactions of Early Lanthanide Metal Atoms (Nd, Sm, Eu) with Water Molecules. A Matrix Isolation Infrared Spectroscopic and Theoretical Study. The Journal of Physical Chemistry A. 2006-09, 110 (36): 10575–10582 [2019-10-26]. ISSN 1089-5639. doi:10.1021/jp063776g. （原始内容存档于2020-08-01）（英语）.

[14] [14]
无机化学丛书. pp 210-215. 2. 卤素化合物

[15] [15]
Emel'yanov, V. I.; Kuznetsova, L. I.; Abramova, L. V.; Ezhov, A. I. Systems Eu₂O₃-HI-H₂O and EuI₃-HI-H₂O at 25°C. Zhurnal Neorganicheskoi Khimii, 1997. 42(8): 1394-1396.

[16] [16]
DIAO, Chengpeng; YU, Jinqiu; LI, Hongwei; PENG, Peng; WU, Hao; HE, Huaqiang; YAN, Shihong; HU, Yunsheng. Ammonium-iodide route to anhydrous EuI₂: mechanism and preparation. Journal of Rare Earths. 2015, 33 (11): 1189–1195. ISSN 1002-0721. doi:10.1016/S1002-0721(14)60545-7.

[wucong-Ln2+-17] [17]
无机化学丛书. pp 203. 3. Ln²⁺的水溶液体系.

[18] [18]
无机化合物合成手册. pp 258-259. 819 硫酸盐.

[19] [19]
Koskenlinna, Markus; Niinisto, Lauri. Lanthanoid sulfites. III. Preparation and properties of two isomorphous series of lanthanoid sulfite hydrates. Finnish Chemical Letters, 1975. (3-4): 83-88. ISSN: 0303-4100.

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