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Oxidant-Activated Reactions of Nucleophiles with Silicon Nanocrystals

Dasog, Mita and Thompson, Jonathan R. and Lewis, Nathan S. (2017) Oxidant-Activated Reactions of Nucleophiles with Silicon Nanocrystals. Chemistry of Materials, 29 (16). pp. 7002-7013. ISSN 0897-4756. doi:10.1021/acs.chemmater.7b02572.

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The oxidant-activated reactivity of Si toward nucleophiles was evaluated for Si nanocrystals (Si-NCs) of differing diameters, d. In the presence of ferrocenium as a one-electron, outer-sphere oxidant, d ≥ 8 nm Si-NCs readily reacted with nucleophiles, including methanol, butanol, butylamine, butanoic acid, butylthiol, and diethylphosphine. However, d < 8 nm Si-NCs did not undergo such reactions, and stronger oxidants such as acetylferrocenium or 1,1′-diacetylferrocenium were required. Butylamine-, butylthiol-, and butanol-functionalized d ≥ 8 nm Si-NCs were partially oxidized and exhibited photoluminescence originating from defect states. In contrast, butanoic acid-functionalized Si-NCs were minimally oxidized and displayed core emission resulting from the excitation and relaxation of electrons across the Si-NC bandgap. Diethylphosphine-functionalized Si-NCs were stable only under inert conditions and showed core emission, with the Si–P bonds being highly susceptible to oxidation and rapidly decomposing upon exposure to ambient conditions. The general reactivity is consistent with the redox potential of the one-electron oxidant and the valence band edge position of the Si-NCs. The trends in reactivity thus provide an example of differential chemical reactions of nanoparticles relative to bulk materials, reflecting the differences in electronic structure and the continuum of electronic properties between variously sized Si nanoparticles and bulk Si samples.

Item Type:Article
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URLURL TypeDescription Information
Dasog, Mita0000-0002-7846-3414
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2017 American Chemical Society. Received: June 22, 2017; Revised: June 30, 2017; Published: July 11, 2017. The authors acknowledge the National Science Foundation (Grant CHE-1214152) and Dalhousie University for providing financial support. Instrumentation support was provided by the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology and by the Institute for Research in Materials at Dalhousie University. M.D. acknowledges a postdoctoral fellowship from the National Sciences and Engineering Research Council of Canada. J.R.T. acknowledges support from the U.S. Department of Energy “Light-Material Interactions in Energy Conversion” Energy Frontier Research Center under Grant DE-SC0001293. We thank Dr. A. C. Nielander and Azhar Carim for insightful discussions during the preparation of this work. The authors declare no competing financial interest.
Funding AgencyGrant Number
Dalhousie UniversityUNSPECIFIED
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Department of Energy (DOE)DE-SC0001293
Issue or Number:16
Record Number:CaltechAUTHORS:20170814-133810210
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Official Citation:Oxidant-Activated Reactions of Nucleophiles with Silicon Nanocrystals Mita Dasog, Jonathan R. Thompson, and Nathan S. Lewis Chemistry of Materials 2017 29 (16), 7002-7013 DOI: 10.1021/acs.chemmater.7b02572
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:80366
Deposited By: George Porter
Deposited On:14 Aug 2017 20:53
Last Modified:15 Nov 2021 19:30

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