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Article

Direct Solvothermal Synthesis of Early Transition Metal Nitrides

Supporting Info

Baishakhi Mazumder, Pietro Chirico and Andrew L. Hector*

School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom

Inorg. Chem., 2008, 47 (20), pp 9684–9690

DOI: 10.1021/ic800767m

Publication Date (Web): September 19, 2008

* Author to whom correspondence should be addressed. Phone: +44(0)23 8059 4125. Fax: +44(0)23 8059 6805. E-mail: A.L.Hector@soton.ac.uk.

Abstract

Solvothermal reactions of TaCl₅ with LiNH₂ in benzene result in nanocrystalline Ta₃N₅ at 500 or 550 °C. The ∼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.