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Title: Catalytic activity in lithium-treated core–shell MoOx/MoS2 nanowires

Abstract

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoOx/MoS2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H2 evolution. The 1D nanowires exhibit significant improvement in H2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS2 layers in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [2];  [4];  [2];  [5];  [2]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Louisville, Louisville, KY (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rutgers Univ., Piscataway, NJ (United States)
  4. Rutgers Univ., Piscataway, NJ (United States)
  5. Univ. of Louisville, Louisville, KY (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Energy Information Administration (EIA)
OSTI Identifier:
1255253
Report Number(s):
LA-UR-15-27897
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 40; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN

Citation Formats

Cummins, Dustin R., Martinez, Ulises, Kappera, Rajesh, Voiry, Damien, Martinez-Garcia, Alejandro, Jasinski, Jacek, Kelly, Dan, Chhowalla, Manish, Mohite, Aditya D., Sunkara, Mahendra K., and Gupta, Gautam. Catalytic activity in lithium-treated core–shell MoOx/MoS2 nanowires. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b05640.
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Cummins, Dustin R., Martinez, Ulises, Kappera, Rajesh, Voiry, Damien, Martinez-Garcia, Alejandro, Jasinski, Jacek, Kelly, Dan, Chhowalla, Manish, Mohite, Aditya D., Sunkara, Mahendra K., & Gupta, Gautam. Catalytic activity in lithium-treated core–shell MoOx/MoS2 nanowires. United States. https://doi.org/10.1021/acs.jpcc.5b05640
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Cummins, Dustin R., Martinez, Ulises, Kappera, Rajesh, Voiry, Damien, Martinez-Garcia, Alejandro, Jasinski, Jacek, Kelly, Dan, Chhowalla, Manish, Mohite, Aditya D., Sunkara, Mahendra K., and Gupta, Gautam. Tue . "Catalytic activity in lithium-treated core–shell MoOx/MoS2 nanowires". United States. https://doi.org/10.1021/acs.jpcc.5b05640. https://www.osti.gov/servlets/purl/1255253.
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@article{osti_1255253,
title = {Catalytic activity in lithium-treated core–shell MoOx/MoS2 nanowires},
author = {Cummins, Dustin R. and Martinez, Ulises and Kappera, Rajesh and Voiry, Damien and Martinez-Garcia, Alejandro and Jasinski, Jacek and Kelly, Dan and Chhowalla, Manish and Mohite, Aditya D. and Sunkara, Mahendra K. and Gupta, Gautam},
abstractNote = {Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoOx/MoS2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H2 evolution. The 1D nanowires exhibit significant improvement in H2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS2 layers in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).},
doi = {10.1021/acs.jpcc.5b05640},
journal = {Journal of Physical Chemistry. C},
number = 40,
volume = 119,
place = {United States},
year = {Tue Sep 22 00:00:00 EDT 2015},
month = {Tue Sep 22 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.jpcc.5b05640
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Works referenced in this record:

Hydrogen and synthesis gas by steam- and C02 reforming
journal, January 2002

Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water
journal, August 2002

  • Cortright, R. D.; Davda, R. R.; Dumesic, J. A.
  • Nature, Vol. 418, Issue 6901
  • DOI: 10.1038/nature01009

Partial oxidation of methane to synthesis gas using carbon dioxide
journal, July 1991

  • Ashcroft, A. T.; Cheetham, A. K.; Green, M. L. H.
  • Nature, Vol. 352, Issue 6332
  • DOI: 10.1038/352225a0

Electrolysis of water on (oxidized) metal surfaces
journal, December 2005

Ordered nanoporous arrays of carbon supporting high dispersions of platinum nanoparticles
journal, July 2001

  • Joo, Sang Hoon; Choi, Seong Jae; Oh, Ilwhan
  • Nature, Vol. 412, Issue 6843
  • DOI: 10.1038/35084046

Exfoliated Graphene Separated by Platinum Nanoparticles
journal, November 2008

  • Si, Yongchao; Samulski, Edward T.
  • Chemistry of Materials, Vol. 20, Issue 21
  • DOI: 10.1021/cm801356a

Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
journal, January 2010

  • Sheng, Wenchao; Gasteiger, Hubert A.; Shao-Horn, Yang
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3483106

Scalable Bromide-Triggered Synthesis of Pd@Pt Core–Shell Ultrathin Nanowires with Enhanced Electrocatalytic Performance toward Oxygen Reduction Reaction
journal, June 2015

  • Li, Hui-Hui; Ma, Si-Yue; Fu, Qi-Qi
  • Journal of the American Chemical Society, Vol. 137, Issue 24
  • DOI: 10.1021/jacs.5b03877

Preparation and Photocatalytic Behavior of MoS 2 and WS 2 Nanocluster Sensitized TiO 2
journal, July 2004

  • Ho, Wingkei; Yu, Jimmy C.; Lin, Jun
  • Langmuir, Vol. 20, Issue 14
  • DOI: 10.1021/la049838g

Photoelectrochemical properties of chemically exfoliated MoS2
journal, January 2013

  • King, Laurie A.; Zhao, Weijie; Chhowalla, Manish
  • Journal of Materials Chemistry A, Vol. 1, Issue 31
  • DOI: 10.1039/c3ta11633f

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013

  • Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki
  • Nature Chemistry, Vol. 5, Issue 4, p. 263-275
  • DOI: 10.1038/nchem.1589

Conducting MoS 2 Nanosheets as Catalysts for Hydrogen Evolution Reaction
journal, November 2013

  • Voiry, Damien; Salehi, Maryam; Silva, Rafael
  • Nano Letters, Vol. 13, Issue 12
  • DOI: 10.1021/nl403661s

Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution
journal, July 2013

  • Voiry, Damien; Yamaguchi, Hisato; Li, Junwen
  • Nature Materials, Vol. 12, Issue 9
  • DOI: 10.1038/nmat3700

Biomimetic Hydrogen Evolution:  MoS 2 Nanoparticles as Catalyst for Hydrogen Evolution
journal, April 2005

  • Hinnemann, Berit; Moses, Poul Georg; Bonde, Jacob
  • Journal of the American Chemical Society, Vol. 127, Issue 15
  • DOI: 10.1021/ja0504690

Core–shell MoO3–MoS2 Nanowires for Hydrogen Evolution A Functional Design for Electrocatalytic Materials
journal, October 2011

  • Chen, Zhebo; Cummins, Dustin; Reinecke, Benjamin N.
  • Nano Letters, Vol. 11, Issue 10, p. 4168-4175
  • DOI: 10.1021/nl2020476

Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts
journal, July 2007

  • Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.
  • Science, Vol. 317, Issue 5834, p. 100-102
  • DOI: 10.1126/science.1141483

Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis
journal, October 2012

  • Kibsgaard, Jakob; Chen, Zhebo; Reinecke, Benjamin N.
  • Nature Materials, Vol. 11, Issue 11, p. 963-969
  • DOI: 10.1038/nmat3439

Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials
journal, October 2014

  • Benck, Jesse D.; Hellstern, Thomas R.; Kibsgaard, Jakob
  • ACS Catalysis, Vol. 4, Issue 11
  • DOI: 10.1021/cs500923c

Amorphous Molybdenum Sulfide Catalysts for Electrochemical Hydrogen Production: Insights into the Origin of their Catalytic Activity
journal, August 2012

  • Benck, Jesse D.; Chen, Zhebo; Kuritzky, Leah Y.
  • ACS Catalysis, Vol. 2, Issue 9, p. 1916-1923
  • DOI: 10.1021/cs300451q

MoS2 Nanoparticles Grown on Graphene An Advanced Catalyst for the Hydrogen Evolution Reaction
journal, May 2011

  • Li, Yanguang; Wang, Hailiang; Xie, Liming
  • Journal of the American Chemical Society, Vol. 133, Issue 19, p. 7296-7299
  • DOI: 10.1021/ja201269b

Electrochemical Tuning of MoS 2 Nanoparticles on Three-Dimensional Substrate for Efficient Hydrogen Evolution
journal, April 2014

  • Wang, Haotian; Lu, Zhiyi; Kong, Desheng
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn500959v

Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers
journal, February 2013

  • Kong, Desheng; Wang, Haotian; Cha, Judy J.
  • Nano Letters, Vol. 13, Issue 3, p. 1341-1347
  • DOI: 10.1021/nl400258t

MoS 2 Nanosheets: A Designed Structure with High Active Site Density for the Hydrogen Evolution Reaction
journal, August 2013

  • Wu, Zhuangzhi; Fang, Baizeng; Wang, Zhiping
  • ACS Catalysis, Vol. 3, Issue 9
  • DOI: 10.1021/cs400384h

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction
journal, November 2013

  • Wang, H.; Lu, Z.; Xu, S.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 49
  • DOI: 10.1073/pnas.1316792110

Enhanced Hydrogen Evolution Catalysis from Chemically Exfoliated Metallic MoS 2 Nanosheets
journal, May 2013

  • Lukowski, Mark A.; Daniel, Andrew S.; Meng, Fei
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja404523s

Highly active hydrogen evolution catalysis from metallic WS 2 nanosheets
journal, January 2014

  • Lukowski, Mark A.; Daniel, Andrew S.; English, Caroline R.
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE01329H

Tuning the MoS 2 Edge-Site Activity for Hydrogen Evolution via Support Interactions
journal, February 2014

  • Tsai, Charlie; Abild-Pedersen, Frank; Nørskov, Jens K.
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl404444k

Nickel/Nickel(II) Oxide Nanoparticles Anchored onto Cobalt(IV) Diselenide Nanobelts for the Electrochemical Production of Hydrogen
journal, July 2013

  • Xu, Yun-Fei; Gao, Min-Rui; Zheng, Ya-Rong
  • Angewandte Chemie International Edition, Vol. 52, Issue 33
  • DOI: 10.1002/anie.201303495

Structure-Function Relations in Molybdenum Sulfide Catalysts: The "Rim-Edge" Model
journal, October 1994

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation
journal, January 2015

  • Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6982

The reactivity of MoS2 single crystal edge planes
journal, March 1985

One-Dimensional Metallic Edge States in MoS 2
journal, October 2001

Structure, Energetics, and Electronic Properties of the Surface of a Promoted MoS2 Catalyst: An ab Initio Local Density Functional Study
journal, February 2000

Ab Initio Study of the H2–H2S/MoS2 Gas–Solid Interface: The Nature of the Catalytically Active Sites
journal, January 2000

Electronic structure of MoSe 2 , MoS 2 , and WSe 2 . I. Band-structure calculations and photoelectron spectroscopy
journal, April 1987

Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials
journal, February 2011

Atomically Thin MoS2 A New Direct-Gap Semiconductor
journal, September 2010

Structural destabilization induced by lithium intercalation in MoS 2 and related compounds
journal, January 1983

  • Py, M. A.; Haering, R. R.
  • Canadian Journal of Physics, Vol. 61, Issue 1
  • DOI: 10.1139/p83-013

Single-layer MoS2
journal, April 1986

MoS2 and WS2 Analogues of Graphene
journal, April 2010

  • Ramakrishna Matte, H. S. S.; Gomathi, A.; Manna, Arun K.
  • Angewandte Chemie International Edition, Vol. 49, Issue 24
  • DOI: 10.1002/anie.201000009

Coherent Atomic and Electronic Heterostructures of Single-Layer MoS2
journal, July 2012

  • Eda, Goki; Fujita, Takeshi; Yamaguchi, Hisato
  • ACS Nano, Vol. 6, Issue 8, p. 7311-7317
  • DOI: 10.1021/nn302422x

Photoluminescence from Chemically Exfoliated MoS2
journal, December 2011

  • Eda, Goki; Yamaguchi, Hisato; Voiry, Damien
  • Nano Letters, Vol. 11, Issue 12, p. 5111-5116
  • DOI: 10.1021/nl201874w

Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries
journal, October 2013

Dilatometric Investigations of Graphite Electrodes in Nonaqueous Lithium Battery Electrolytes
journal, January 2000

  • Winter, Martin; Wrodnigg, Gerhard H.; Besenhard, Jürgen O.
  • Journal of The Electrochemical Society, Vol. 147, Issue 7, p. 2427-2431
  • DOI: 10.1149/1.1393548

Hydrogen Evolution Reaction on Copper, Gold, Molybdenum, Palladium, Rhodium, and Iron
journal, January 1957

  • Pentland, N.; Bockris, J. O'M.; Sheldon, E.
  • Journal of The Electrochemical Society, Vol. 104, Issue 3
  • DOI: 10.1149/1.2428530

Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H
journal, August 2002

High-Performance Electrocatalysis Using Metallic Cobalt Pyrite (CoS 2 ) Micro- and Nanostructures
journal, June 2014

  • Faber, Matthew S.; Dziedzic, Rafal; Lukowski, Mark A.
  • Journal of the American Chemical Society, Vol. 136, Issue 28
  • DOI: 10.1021/ja504099w

From Bulk to Monolayer MoS2: Evolution of Raman Scattering
journal, January 2012

  • Li, Hong; Zhang, Qing; Yap, Chin Chong Ray
  • Advanced Functional Materials, Vol. 22, Issue 7
  • DOI: 10.1002/adfm.201102111

Raman and resonance Raman investigation of MoS 2 nanoparticles
journal, July 1999

  • Frey, Gitti L.; Tenne, Reshef; Matthews, Manyalibo J.
  • Physical Review B, Vol. 60, Issue 4
  • DOI: 10.1103/PhysRevB.60.2883

Li intercalation across and along the van der Waals surfaces of MoS2(0001)
journal, September 1995

Structure of Restacked MoS 2 and WS 2 Elucidated by Electron Crystallography
journal, February 1999

  • Heising, Joy; Kanatzidis, Mercouri G.
  • Journal of the American Chemical Society, Vol. 121, Issue 4
  • DOI: 10.1021/ja983043c
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    • Nature Communications, Vol. 7, Issue 1
    • DOI: 10.1038/ncomms11857

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    journal, November 2018

    • Mandal, Debasish; Routh, Parimal; Nandi, Arun K.
    • Chemistry - An Asian Journal, Vol. 13, Issue 24
    • DOI: 10.1002/asia.201801173

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    journal, February 2016

    • Voiry, Damien; Yang, Jieun; Chhowalla, Manish
    • Advanced Materials, Vol. 28, Issue 29
    • DOI: 10.1002/adma.201505597

    Facile Synthesis of Molybdenum Diselenide Layers for High-Performance Hydrogen Evolution Electrocatalysts
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