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© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.

Abstract

Herein, we report the mechanistic investigation of the formation of nickel (Ni) nanocrystallites during the formation of amorphous silicon nitride at a temperature as low as 400 °C, using perhydropolysilazane (PHPS) as a preformed precursor and further coordinated by nickel chloride (NiCl2); thus, forming the non-noble transition metal (TM) as a potential catalyst and the support in an one-step process. It was demonstrated that NiCl2 catalyzed dehydrocoupling reactions between Si-H and N-H bonds in PHPS to afford ternary silylamino groups, which resulted in the formation of a nanocomposite precursor via complex formation: Ni(II) cation of NiCl2 coordinated the ternary silylamino ligands formed in situ. By monitoring intrinsic chemical reactions during the precursor pyrolysis under inert gas atmosphere, it was revealed that the Ni-N bond formed by a nucleophilic attack of the N atom on the Ni(II) cation center, followed by Ni nucleation below 300 °C, which was promoted by the decomposition of Ni nitride species. The latter was facilitated under the hydrogen-containing atmosphere generated by the NiCl2-catalyzed dehydrocoupling reaction. The increase of the temperature to 400 °C led to the formation of a covalently-bonded amorphous Si3N4 matrix surrounding Ni nanocrystallites.

Details

Title
Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
Author
Asakuma, Norifumi 1 ; Tada, Shotaro 1   VIAFID ORCID Logo  ; Kawaguchi, Erika 1 ; Terashima, Motoharu 1 ; Honda, Sawao 1   VIAFID ORCID Logo  ; Rafael Kenji Nishihora 2 ; Carles, Pierre 2 ; Bernard, Samuel 2   VIAFID ORCID Logo  ; Iwamoto, Yuji 1   VIAFID ORCID Logo 

 Department of Life Science and Applied Chemistry, Graduated School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan; [email protected] (N.A.); [email protected] (S.T.); [email protected] (E.K.); [email protected] (M.T.); [email protected] (S.H.) 
 CNRS, IRCER, UMR 7315, University of Limoges, F-87000 Limoges, France; [email protected] (R.K.N.); [email protected] (P.C.); [email protected] (S.B.) 
First page
1644
Publication year
2022
Publication date
2022
Publisher
MDPI AG
e-ISSN
20794991
Source type
Scholarly Journal
Language of publication
English
ProQuest document ID
2670340060
Copyright
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.