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Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites

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 (NiCl(2)); thus,...

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Autores principales: Asakuma, Norifumi, Tada, Shotaro, Kawaguchi, Erika, Terashima, Motoharu, Honda, Sawao, Nishihora, Rafael Kenji, Carles, Pierre, Bernard, Samuel, Iwamoto, Yuji
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9145008/
https://www.ncbi.nlm.nih.gov/pubmed/35630866
http://dx.doi.org/10.3390/nano12101644
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author Asakuma, Norifumi
Tada, Shotaro
Kawaguchi, Erika
Terashima, Motoharu
Honda, Sawao
Nishihora, Rafael Kenji
Carles, Pierre
Bernard, Samuel
Iwamoto, Yuji
author_facet Asakuma, Norifumi
Tada, Shotaro
Kawaguchi, Erika
Terashima, Motoharu
Honda, Sawao
Nishihora, Rafael Kenji
Carles, Pierre
Bernard, Samuel
Iwamoto, Yuji
author_sort Asakuma, Norifumi
collection PubMed
description 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 (NiCl(2)); thus, forming the non-noble transition metal (TM) as a potential catalyst and the support in an one-step process. It was demonstrated that NiCl(2) 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 NiCl(2) 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 NiCl(2)-catalyzed dehydrocoupling reaction. The increase of the temperature to 400 °C led to the formation of a covalently-bonded amorphous Si(3)N(4) matrix surrounding Ni nanocrystallites.
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spelling pubmed-91450082022-05-29 Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites Asakuma, Norifumi Tada, Shotaro Kawaguchi, Erika Terashima, Motoharu Honda, Sawao Nishihora, Rafael Kenji Carles, Pierre Bernard, Samuel Iwamoto, Yuji Nanomaterials (Basel) Article 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 (NiCl(2)); thus, forming the non-noble transition metal (TM) as a potential catalyst and the support in an one-step process. It was demonstrated that NiCl(2) 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 NiCl(2) 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 NiCl(2)-catalyzed dehydrocoupling reaction. The increase of the temperature to 400 °C led to the formation of a covalently-bonded amorphous Si(3)N(4) matrix surrounding Ni nanocrystallites. MDPI 2022-05-11 /pmc/articles/PMC9145008/ /pubmed/35630866 http://dx.doi.org/10.3390/nano12101644 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/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/).
spellingShingle Article
Asakuma, Norifumi
Tada, Shotaro
Kawaguchi, Erika
Terashima, Motoharu
Honda, Sawao
Nishihora, Rafael Kenji
Carles, Pierre
Bernard, Samuel
Iwamoto, Yuji
Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
title Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
title_full Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
title_fullStr Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
title_full_unstemmed Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
title_short Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites
title_sort mechanistic investigation of the formation of nickel nanocrystallites embedded in amorphous silicon nitride nanocomposites
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9145008/
https://www.ncbi.nlm.nih.gov/pubmed/35630866
http://dx.doi.org/10.3390/nano12101644
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