title: Solid-State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles.
abstract: Silicon nanoparticles (NPs) serve a wide range of optical, electronic, and biological applications. Chemical grafting of various molecules to Si NPs can help to passivate their reactive surfaces, "fine-tune" their properties, or even give them further interesting features. In this work, (1) H, (13) C, and (29) Si solid-state NMR spectroscopy has been combined with density functional theory calculations to study the surface chemistry of hydride-terminated and alkyl-functionalized Si NPs. This combination of techniques yields assignments for the observed chemical shifts, including the contributions resulting from different surface planes, and highlights the presence of physisorbed water. Resonances from near-surface (13) C nuclei were shown to be substantially broadened due to surface disorder and it is demonstrated that in an ambient environment hydride-terminated Si NPs undergo fast back-bond oxidation, whereas long-chain alkyl-functionalized Si NPs undergo slow oxidation. Furthermore, the combination of NMR spectroscopy and DFT calculations showed that the employed hydrosilylation reaction involves anti-Markovnikov addition of the 1-alkene to the surface of the Si NPs.
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).
authors.forename: Daniel
authors.initials: D
authors.lastname: Lee
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).|Present address: Institutes of Biophysical Chemistry, Physical and Theoretical Chemistry and Center for Biomolecular Magnetic Resonance BMRZ, Goethe University Frankfurt, 60438 Frankfurt/M. (Germany).
authors.forename: Monu
authors.initials: M
authors.lastname: Kaushik
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).|Present address: Université de Lorraine, LCPME, UMR 7564, Villers-les-Nancy 54600 (France).
authors.forename: Romain
authors.initials: R
authors.lastname: Coustel
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).
authors.forename: Yves
authors.initials: Y
authors.lastname: Chenavier
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).
authors.forename: Myriam
authors.initials: M
authors.lastname: Chanal
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).
authors.forename: Michel
authors.initials: M
authors.lastname: Bardet
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).
authors.forename: Lionel
authors.initials: L
authors.lastname: Dubois
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SP2M, 38000 Grenoble (France).
authors.forename: Hanako
authors.initials: H
authors.lastname: Okuno
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA-LETI, MINATEC Campus, 38054 Grenoble (France).
authors.forename: Névine
authors.initials: N
authors.lastname: Rochat
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France).|CEA, INAC, SCIB, 38000 Grenoble (France).
authors.forename: Florence
authors.initials: F
authors.lastname: Duclairoir
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France). jean-marie.mouesca@cea.fr.|CEA, INAC, SCIB, 38000 Grenoble (France). jean-marie.mouesca@cea.fr.
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Mouesca
authors.affiliation: Univsité Grenoble Alpes, 38000 Grenoble (France). gael.depaepe@cea.fr.|CEA, INAC, SCIB, 38000 Grenoble (France). gael.depaepe@cea.fr.
authors.forename: Gaël
authors.initials: G
authors.lastname: De Paëpe
keywords: NMR spectroscopy; density functional theory; hydrosilylation; nanoparticles; silicon