Solid-State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles - Université de Lorraine Access content directly
Journal Articles Chemistry - A European Journal Year : 2015

Solid-State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles

Daniel Lee
Monu Kaushik
  • Function : Author
Romain Coustel
Michel Bardet
Jean-Marie Mouesca
Gaël de Paëpe

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, H-1, C-13, and Si-29 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 C-13 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.

Dates and versions

hal-01507024 , version 1 (12-04-2017)

Identifiers

Cite

Daniel Lee, Monu Kaushik, Romain Coustel, Yves Chenavier, Myriam Chanal, et al.. Solid-State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles. Chemistry - A European Journal, 2015, 21 (45), pp.16047-16058. ⟨10.1002/chem.201502687⟩. ⟨hal-01507024⟩
682 View
0 Download

Altmetric

Share

Gmail Facebook X LinkedIn More