CaltechAUTHORS
  A Caltech Library Service

Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS₂ and MoS₂

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

This is the latest version of this item.

[img] PDF - Supplemental Material
See Usage Policy.

1MB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20220216-289231016

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
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acsami.1c20949DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acsami.1c20949/suppl_file/am1c20949_si_001.pdfPublisherSupporting Information
ORCID:
AuthorORCID
Yan, Ellen0000-0003-3252-790X
Morla, Maureen B.0000-0002-2520-9543
Kwon, Soonho0000-0002-9225-3018
Musgrave, Charles B.0000-0002-3432-0817
Brunschwig, Bruce S.0000-0002-6135-6727
Goddard, William A., III0000-0003-0097-5716
Lewis, Nathan S.0000-0001-5245-0538
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
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-03ER15483
Weizmann Institute of ScienceUNSPECIFIED
Zuckerman STEM Leadership ProgramUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Department of Energy (DOE)DE-SC0021266
Subject Keywords:density functional theory; grand canonical electrocatalysis; transition metal dichalcogenide; surface functionalization; potential-dependent reaction
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:18 May 2022 15:57

Available Versions of this Item

  • Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS₂ and MoS₂. (deposited 16 Feb 2022 10:04) [Currently Displayed]

Commentary/Response Threads

  • 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]

Repository Staff Only: item control page