化学学报 ›› 1991, Vol. 49 ›› Issue (4): 329-334. 上一篇    下一篇

研究论文

温和条件下稀土氯化物-萘催化的碱金属氢化物的合成

张一平;廖世健;徐筠;王美君;樊明兵;沈琪   

  1. 中国科学院大连化学物理研究所.大连(116012);中国科学院长春应用化学研究 所.长春(130022)
  • 发布日期:1991-04-15

Synthesis of alkali metal hydrides using lanthanide trichloride- naphthalene as catalyst under mild conditions

Zhang Yiping;Liao Shijian;Xu Yun;Wang Meijun;Fan Mingbing;Shen Qi   

  1. Dalian Inst Chem Phys, CAS.Dalian(116012);Changchun Inst Appl Chem., CAS.Changchun(130022)
  • Published:1991-04-15

本文研究了稀土氯化物对碱金属氢化反应的催化作用。金属钠在稀土氯化物LnCl~3(Ln=La,Nd,Sm,Dy,Yb)和萘的催化下,在常压、40℃下能与氢气反应,生成氢化钠;稀土氯化物的催化活性顺序为LaCl~3>NdCl~3>SmCl~3>DyCl~3>YbCl~3。金属锂可发生类似反应,生成LiH;但其反应动力学曲线与金属钠相比明显不同。稀土氯化物对金属钾的氢化反应不显示催化作用。对反应机理的初步探索表明:碱金属与萘反应生成的阴离子自由基型物种可能是氢化反应的中间体,稀土氯化物的作用是催化该中间体的氢化反应。该反应的产物是一类大比表面积(NaH的比表面积为83m^2/g)、多孔性固体粉末,在空气中可自燃。它们具有比一般市售碱金属氢化物高得多的反应活性,并能与过渡金属配合物组成高活性烯烃加氢催化。

关键词: 金属氢化物, 碱金属, 萘, 稀土氯化物, 催化作用, 氢化反应, 金属钠, 氢化钠,

The hydrogenation of alkali metals using lanthanide trichloride and naphthalene as catalyst has been studied. LnCl~3 (Ln=Na, Nd, Sm, Dy, Yb) and naphthalene can catalyze the hydrogenation of sodium under atmospheric pressure and 40℃ to form sodium hydride. The activities of lanthanide trichlorides are in the following order: LaCl~3>NdCl~3>SmCl~3>DyCl~3>YbCl~3. Although lithium proceeds in the same catalytic reaction, the kinetic curve of the lithium hydrogenation is different from that of sodium. Lanthanide trichlorides display no catalytic effect on the hydrogenation of potassium in presence of naphthalene. The mechanism of this reaction has been studied and it is suggested that the anion-radical of alkali metal naphthalene complexes may be the intermediate for the hydrogenation of alkali metals and the function of LnCl~3 is to catalyze the hydrogenation of the intermediate. The products are porous solids with high specific surface area (83m^2/g for NaH) and pyrophoric in air. They are far more active than the commercial alkali metal hydrides. The combination of these hydrides with some transition metal complexes exhibits high catalytic activity for the hydrogenation of olefins.

Key words: METAL HYDRIDE, ALKALI METAL, NAPHTHALENE, CATALYTIC EFFECT, SODIUM HYDRIDE, HYDROGEN

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