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Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS₂

Yan, Ellen X. and Cabán-Acevedo, Miguel and Papadantonakis, Kimberly M. and Brunschwig, Bruce S. and Lewis, Nathan S. (2020) Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS₂. ACS Materials Letters, 2 (2). pp. 133-139. ISSN 2639-4979. doi:10.1021/acsmaterialslett.9b00241.

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Recently developed covalent functionalization chemistry for MoS₂ in the 1T′ phase enables the formation of covalent chalcogenide–carbon bonds from alkyl halides and aryl diazonium salts. However, the coverage of functional groups using this method has been limited by the amount of negative charge stored in the exfoliated MoS₂ sheets to <25–30% per MoS₂ unit. We report, herein, a reductant-activated functionalization, wherein one-electron metallocene reductants, such as nickelocene, octamethylnickelocene, and cobaltocene, are introduced during functionalization with methyl and propyl halides to tune the coverage of the alkyl groups. The reductant-activated functionalization yields functional group coverages up to 70%, ∼1.5–2 times higher than the previous limit, and enables functionalization by weak electrophiles, such as 1-chloropropane, that are otherwise unreactive with chemically exfoliated MoS₂. We also explored the dependence of coverage on the strength of the leaving group and the steric hindrance of the alkyl halide in the absence of reductants and showed that functionalization was ineffective for chloride leaving groups and for secondary and tertiary alkyl iodides. These results demonstrate a substantial increase in coverage compared to functionalization without reductants, and may impact the performance of these materials in applications reliant on surface interactions. Furthermore, this method may be applicable to the covalent functionalization of similar layered materials and metal chalcogenides.

Item Type:Article
Related URLs:
URLURL TypeDescription
Yan, Ellen X.0000-0003-3252-790X
Papadantonakis, Kimberly M.0000-0002-9900-5500
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2019 American Chemical Society. Received: June 27, 2019; Accepted: December 20, 2019; Published: December 20, 2019. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences under award no. DE-FG02-03ER15483. E.X.Y. gratefully acknowledges Dr. Sonjong Hwang at the Caltech Solid-State NMR Facility for discussions and NMR spectra. Research was in part carried out at the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology. Computations were performed with assistance from the Goddard group at Caltech. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-03ER15483
Issue or Number:2
Record Number:CaltechAUTHORS:20191224-093208052
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Official Citation:Reductant-Activated, High-Coverage, Covalent Functionalization of 1T′-MoS2 Ellen X. Yan, Miguel Cabán-Acevedo, Kimberly M. Papadantonakis, Bruce S. Brunschwig, and Nathan S. Lewis. ACS Materials Letters 2020 2 (2), 133-139; DOI: 10.1021/acsmaterialslett.9b00241
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:100432
Deposited By: George Porter
Deposited On:24 Dec 2019 18:34
Last Modified:16 Nov 2021 17:54

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