Direct Solvothermal Synthesis of Early Transition Metal Nitrides

作者：Mazumder Baishakhi; Chirico Pietro; Hector Andrew L^*

来源：Inorganic Chemistry, 2008, 47(20): 9684-9690.

DOI：10.1021/ic800767m

Solvothermal reactions of TaCl5 with LiNH2 in benzene result in nanocrystalline Ta3N5 at 500 or 550 degrees C. The similar to 25 nm Ta3N5 particles have a band gap of 2.08-2.10 eV. The same reactions in mesitylene resulted in a higher crystallization temperature and large amounts of carbon incorporation due to solvent decomposition. Reactions of Ta(NMe2)(5) with LiNH2 under the same conditions resulted in TaN. Rocksalt-type MN phases are obtained for Zr, Hf, or Nb when their chlorides (ZrCl4, HfCl4, or NbCl5) or dialkylamides (M(NEtMe)(4), M = Zr, Hf) are reacted with LiNH2 under similar conditions. With the amides, there is some evidence for nitrogen-rich compositions (HfN>1), and carbon is incorporated into the products through pyrolysis of the dialkylamide groups.

• 出版日期2008-10-20