Enhancing Hydrogen Evolution Activity of Monolayer Molybdenum Disulfide via a Molecular Proton Mediator

Xiangye Liu; Baichang Li; Fernando A. Soto; Xufan Li; Raymond R. Unocic; Perla B. Balbuena; Avetik R. Harutyunyan; James Hone; Daniel V. Esposito

doi:10.1021/acscatal.1c03016

Enhancing Hydrogen Evolution Activity of Monolayer Molybdenum Disulfide via a Molecular Proton Mediator

Xiangye Liu, Baichang Li, Fernando A. Soto, Xufan Li, Raymond R. Unocic, Perla B. Balbuena, Avetik R. Harutyunyan, James Hone, Daniel V. Esposito

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

The configuration and local environment of active sites in transition metal dichalcogenides can significantly alter their electrocatalytic activity toward the hydrogen evolution reaction (HER). Herein, we demonstrate that the HER activity of monolayer MoS₂electrocatalysts can be enhanced through the modulation of active sites by introducing a molecular mediator that alters the coverage of adsorbed protons. Sodium dodecyl sulfate (SDS) promotes the intrinsic HER activity of both terrace-based sulfur vacancies (V_S) and edge sites during HER operation in an acidic environment, leading to increases in the turnover frequency (TOF) of both sites by up to 5 orders of magnitude. Simulations indicate that SDS facilitates proton adsorption by catching protons from hydronium ions and releasing them to V_S, which reduces the energy barrier by creating a stair-case-like free energy profile. Our results highlight the ability to tailor the activity of electrocatalysts by synergistically combining proton transfer mediators with engineered active sites.

Original language	English
Pages (from-to)	12159-12169
Number of pages	11
Journal	ACS Catalysis
Volume	11
Issue number	19
DOIs	https://doi.org/10.1021/acscatal.1c03016
State	Published - Oct 1 2021

Funding

Primary funding for this research was provided, in part, by Honda Research Institute USA Incorporated. Materials synthesis and sample fabrication were supported by the NSF MRSEC Program through the Center for Precision Assembly of Superstratic and Superatomic Solids (DMR-1420634). STEM characterization was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. Microfocused XPS measurement was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. Macrofocused XPS measurement was performed at Prof. Jingguang Chen’s Lab, and all authors acknowledge Brian Tackett’s work in collecting and processing the corresponding XPS data. F.A.S. and P.B.B. gratefully acknowledge computational resources from Texas A&M High Performance Research Computing and from Texas Advanced Computing Center at UT Austin.

Keywords

MoS2
electrochemical activation
hydrogen evolution reaction
molecular mediator
proton transfer
proton transfer
sodium dodecyl sulfate (SDS)

Access to Document

10.1021/acscatal.1c03016

Cite this

@article{e27f8cdcf50a4f1ebcae80996a0604f9,

title = "Enhancing Hydrogen Evolution Activity of Monolayer Molybdenum Disulfide via a Molecular Proton Mediator",

abstract = "The configuration and local environment of active sites in transition metal dichalcogenides can significantly alter their electrocatalytic activity toward the hydrogen evolution reaction (HER). Herein, we demonstrate that the HER activity of monolayer MoS2electrocatalysts can be enhanced through the modulation of active sites by introducing a molecular mediator that alters the coverage of adsorbed protons. Sodium dodecyl sulfate (SDS) promotes the intrinsic HER activity of both terrace-based sulfur vacancies (VS) and edge sites during HER operation in an acidic environment, leading to increases in the turnover frequency (TOF) of both sites by up to 5 orders of magnitude. Simulations indicate that SDS facilitates proton adsorption by catching protons from hydronium ions and releasing them to VS, which reduces the energy barrier by creating a stair-case-like free energy profile. Our results highlight the ability to tailor the activity of electrocatalysts by synergistically combining proton transfer mediators with engineered active sites.",

keywords = "MoS2, electrochemical activation, hydrogen evolution reaction, molecular mediator, proton transfer, proton transfer, sodium dodecyl sulfate (SDS)",

author = "Xiangye Liu and Baichang Li and Soto, {Fernando A.} and Xufan Li and Unocic, {Raymond R.} and Balbuena, {Perla B.} and Harutyunyan, {Avetik R.} and James Hone and Esposito, {Daniel V.}",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society",

year = "2021",

month = oct,

day = "1",

doi = "10.1021/acscatal.1c03016",

language = "English",

volume = "11",

pages = "12159--12169",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Enhancing Hydrogen Evolution Activity of Monolayer Molybdenum Disulfide via a Molecular Proton Mediator

AU - Liu, Xiangye

AU - Li, Baichang

AU - Soto, Fernando A.

AU - Li, Xufan

AU - Unocic, Raymond R.

AU - Balbuena, Perla B.

AU - Harutyunyan, Avetik R.

AU - Hone, James

AU - Esposito, Daniel V.

PY - 2021/10/1

Y1 - 2021/10/1

N2 - The configuration and local environment of active sites in transition metal dichalcogenides can significantly alter their electrocatalytic activity toward the hydrogen evolution reaction (HER). Herein, we demonstrate that the HER activity of monolayer MoS2electrocatalysts can be enhanced through the modulation of active sites by introducing a molecular mediator that alters the coverage of adsorbed protons. Sodium dodecyl sulfate (SDS) promotes the intrinsic HER activity of both terrace-based sulfur vacancies (VS) and edge sites during HER operation in an acidic environment, leading to increases in the turnover frequency (TOF) of both sites by up to 5 orders of magnitude. Simulations indicate that SDS facilitates proton adsorption by catching protons from hydronium ions and releasing them to VS, which reduces the energy barrier by creating a stair-case-like free energy profile. Our results highlight the ability to tailor the activity of electrocatalysts by synergistically combining proton transfer mediators with engineered active sites.

AB - The configuration and local environment of active sites in transition metal dichalcogenides can significantly alter their electrocatalytic activity toward the hydrogen evolution reaction (HER). Herein, we demonstrate that the HER activity of monolayer MoS2electrocatalysts can be enhanced through the modulation of active sites by introducing a molecular mediator that alters the coverage of adsorbed protons. Sodium dodecyl sulfate (SDS) promotes the intrinsic HER activity of both terrace-based sulfur vacancies (VS) and edge sites during HER operation in an acidic environment, leading to increases in the turnover frequency (TOF) of both sites by up to 5 orders of magnitude. Simulations indicate that SDS facilitates proton adsorption by catching protons from hydronium ions and releasing them to VS, which reduces the energy barrier by creating a stair-case-like free energy profile. Our results highlight the ability to tailor the activity of electrocatalysts by synergistically combining proton transfer mediators with engineered active sites.

KW - MoS2

KW - electrochemical activation

KW - hydrogen evolution reaction

KW - molecular mediator

KW - proton transfer

KW - sodium dodecyl sulfate (SDS)

UR - http://www.scopus.com/inward/record.url?scp=85116031406&partnerID=8YFLogxK

U2 - 10.1021/acscatal.1c03016

DO - 10.1021/acscatal.1c03016

M3 - Article

AN - SCOPUS:85116031406

SN - 2155-5435

VL - 11

SP - 12159

EP - 12169

JO - ACS Catalysis

JF - ACS Catalysis

IS - 19

ER -

Enhancing Hydrogen Evolution Activity of Monolayer Molybdenum Disulfide via a Molecular Proton Mediator

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this