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Catalyst Proximity-Induced Functionalization of h-BN with Quat Derivatives


Hemmi, Adrian; Cun, Huanyao; Tocci, Gabriele; Epprecht, Adrian; Stel, Bart; Lingenfelder, Magalí; de Lima, Luis Henrique; Muntwiler, Matthias; Osterwalder, Jürg; Iannuzzi, Marcella; Greber, Thomas (2019). Catalyst Proximity-Induced Functionalization of h-BN with Quat Derivatives. Nano letters, 19(9):5998-6004.

Abstract

Inert single-layer boron nitride (h-BN) grown on a catalytic metal may be functionalized with quaternary ammonium compounds (quats) that are widely used as nonreactive electrolytes. We observe that the quat treatment, which facilitates the electrochemical transfer of two-dimensional materials, involves a decomposition of quat ions and leads to covalently bound quat derivatives on top of the 2D layer. Applying tetraoctylammonium and h-BN on rhodium, the reaction product is top-alkylized h-BN as identified with high-resolution X-ray photoelectron spectroscopy. The alkyl chains are homogeneously distributed across the surface, and the properties thereof are well-tunable by the choice of different quats. The functionalization further weakens the 2D material–substrate interaction and promotes easy transfer. Therefore, the functionalization scheme that is presented enables the design of 2D materials with tailored properties and with the freedom to position and orient them as required. The mechanism of this functionalization route is investigated with density functional theory calculations, and we identify the proximity of the catalytic metal substrate to alter the chemical reactivity of otherwise inert h-BN layers.

Abstract

Inert single-layer boron nitride (h-BN) grown on a catalytic metal may be functionalized with quaternary ammonium compounds (quats) that are widely used as nonreactive electrolytes. We observe that the quat treatment, which facilitates the electrochemical transfer of two-dimensional materials, involves a decomposition of quat ions and leads to covalently bound quat derivatives on top of the 2D layer. Applying tetraoctylammonium and h-BN on rhodium, the reaction product is top-alkylized h-BN as identified with high-resolution X-ray photoelectron spectroscopy. The alkyl chains are homogeneously distributed across the surface, and the properties thereof are well-tunable by the choice of different quats. The functionalization further weakens the 2D material–substrate interaction and promotes easy transfer. Therefore, the functionalization scheme that is presented enables the design of 2D materials with tailored properties and with the freedom to position and orient them as required. The mechanism of this functionalization route is investigated with density functional theory calculations, and we identify the proximity of the catalytic metal substrate to alter the chemical reactivity of otherwise inert h-BN layers.

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Additional indexing

Item Type:Journal Article, refereed, further contribution
Communities & Collections:07 Faculty of Science > Physics Institute
Dewey Decimal Classification:530 Physics
Scopus Subject Areas:Physical Sciences > Bioengineering
Physical Sciences > General Chemistry
Physical Sciences > General Materials Science
Physical Sciences > Condensed Matter Physics
Physical Sciences > Mechanical Engineering
Uncontrolled Keywords:Mechanical Engineering, General Materials Science, Bioengineering, General Chemistry, Condensed Matter Physics
Language:English
Date:11 September 2019
Deposited On:17 Oct 2019 06:01
Last Modified:29 Jul 2020 11:28
Publisher:American Chemical Society (ACS)
ISSN:1530-6984
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.nanolett.9b01792
Project Information:
  • : FunderSNSF
  • : Grant IDCRSI22_122703
  • : Project TitleBoron nitride nanomesh as a template for guided self-assembly of molecular arrays
  • : FunderH2020
  • : Grant ID785219
  • : Project TitleGrapheneCore2 - Graphene Flagship Core Project 2

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