Yan, Ellen and Balgley, Renata and Morla, Maureen B. and Kwon, Soonho and Musgrave, Charles B. and Brunschwig, Bruce S. and Goddard, William A., III and Lewis, Nathan S. (2022) Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS₂ and MoS₂. ACS Applied Materials & Interfaces, 14 (7). pp. 9744-9753. ISSN 1944-8244. doi:10.1021/acsami.1c20949. https://resolver.caltech.edu/CaltechAUTHORS:20220216-289231016
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Abstract
Reductant-activated functionalization is shown to enhance the methylation of chemically exfoliated MoS₂ (ceMoS₂) and ceWS₂ by introducing excess negative charge to facilitate a nucleophilic attack reaction. Relative to methylation in the absence of a reductant, the reaction produces a twofold increase in coverage of ceWS₂, from 25 to 52% coverage per WS₂. However, at every potential, the methyl coverage on ceWS₂ was ∼20% lower than that on ceMoS₂. We applied grand canonical density functional theory to show that at constant potential, more negative charge is present on 1T′-MoS₂ than on 1T′-WS₂, making methylation both thermodynamically and kinetically more favorable for 1T′-MoS₂ than 1T′-WS₂. This effect was moderated when the reactions were compared at constant charge, emphasizing the importance of comparing the reactivity of materials at nominally identical electrode potentials.
| Item Type: | Article | ||||||||||||||||
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| Alternate Title: | Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS2 and MoS2 | ||||||||||||||||
| Additional Information: | © 2022 American Chemical Society. Received: October 29, 2021; Accepted: January 19, 2022; Published: February 11, 2022. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-FG02-03ER15483. E.X.Y. would also like to thank Bill Ling for assistance with DLS measurements. R.B. is an Awardee of the Weizmann Institute of Science─National Postdoctoral Award Program for Advancing Women in Science and the Zuckerman STEM Leadership Program. Research was possible only with the use of instrumentation maintained in the Molecular Materials Resource Center of the Beckman Institute of the California Institute of Technology. The computations presented here were conducted on a Caltech high-performance cluster, partially supported by a grant from the Gordon and Betty Moore Foundation. S.K., C.B.M., W.A.G., and the H.P.C. calculations were supported by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub, under award number DE-SC0021266. The authors declare no competing financial interest. | ||||||||||||||||
| Group: | Liquid Sunlight Alliance | ||||||||||||||||
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| Subject Keywords: | density functional theory; grand canonical electrocatalysis; transition metal dichalcogenide; surface functionalization; potential-dependent reaction | ||||||||||||||||
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| Issue or Number: | 7 | ||||||||||||||||
| DOI: | 10.1021/acsami.1c20949 | ||||||||||||||||
| Record Number: | CaltechAUTHORS:20220216-289231016 | ||||||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20220216-289231016 | ||||||||||||||||
| Official Citation: | Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS2 and MoS2. Ellen Yan, Renata Balgley, Maureen B. Morla, Soonho Kwon, Charles B. Musgrave, Bruce S. Brunschwig, William A. Goddard, and Nathan S. Lewis. ACS Applied Materials & Interfaces 2022 14 (7), 9744-9753; DOI: 10.1021/acsami.1c20949 | ||||||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||||
| ID Code: | 113472 | ||||||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||||||
| Deposited By: | George Porter | ||||||||||||||||
| Deposited On: | 16 Feb 2022 10:04 | ||||||||||||||||
| Last Modified: | 12 Oct 2022 03:52 |
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- Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS₂ and MoS₂. (deposited 16 Feb 2022 10:04) [Currently Displayed]
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- Yan, Ellen and Balgley, Renata and Morla, Maureen B. and Kwon, Soonho and Musgrave, Charles B. and Brunschwig, Bruce S. and Goddard, William A., III and Lewis, Nathan S. Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS₂ and MoS₂. (deposited 16 Feb 2022 10:04) [Currently Displayed]
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