Low-temperature Synthesis of Heterostructures of Transition Metal Dichalcogenide Alloys (WxMo1-xS2) and Graphene with Superior Catalytic Performance for Hydrogen Evolution

Yu Lei, Srimanta Pakhira, Kazunori Fujisawa, Xuyang Wang, Oluwagbenga Oare Iyiola, Nestor Perea Lopez, Ana Laura Elias Arriaga, Lakshmy Pulickal Rajukumar, Chanjing Zhou, Bernd C. Kabius, Nasim Alem, Morinobu Endo, Ruitao Lv, Jose L. Mendoza-Cortes, Mauricio Terrones Maldonado

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Abstract

Large-area (∼cm2) films of vertical heterostructures formed by alternating graphene and transition-metal dichalcogenide (TMD) alloys are obtained by wet chemical routes followed by a thermal treatment at low temperature. In particular, we synthesized stacked graphene and WxMo1-xS2 alloy phases that were used as hydrogen evolution catalysts. We observed a Tafel slope of 38.7 mV dec-1 and 96 mV onset potential (at current density of 10 mA cm-2) when the heterostructure alloy was annealed at 300 °C. These results indicate that heterostructures formed by graphene and W0.4Mo0.6S2 alloys are far more efficient than WS2 and MoS2 by at least a factor of 2, and they are superior compared to other reported TMD systems. This strategy offers a cheap and low temperature synthesis alternative able to replace Pt in the hydrogen evolution reaction (HER). Furthermore, the catalytic activity of the alloy is stable over time, i.e., the catalytic activity does not experience a significant change even after 1000 cycles. Using density functional theory calculations, we found that this enhanced hydrogen evolution in the WxMo1-xS2 alloys is mainly due to the lower energy barrier created by a favorable overlap of the d-orbitals from the transition metals and the s-orbitals of H2; with the lowest energy barrier occurring for the W0.4Mo0.6S2 alloy. Thus, it is now possible to further improve the performance of the "inert" TMD basal plane via metal alloying, in addition to the previously reported strategies such as creation of point defects, vacancies and edges. The synthesis of graphene/W0.4Mo0.6S2 produced at relatively low temperatures is scalable and could be used as an effective low cost Pt-free catalyst.

Original languageEnglish (US)
Pages (from-to)5103-5112
Number of pages10
JournalACS Nano
Volume11
Issue number5
DOIs
StatePublished - May 23 2017

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Transition metal alloys
Graphite
Graphene
Heterojunctions
Hydrogen
graphene
transition metals
hydrogen
synthesis
Transition metals
Energy barriers
Temperature
Catalyst activity
catalytic activity
Catalysts
catalysts
orbitals
Point defects
Alloying
Vacancies

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Lei, Yu ; Pakhira, Srimanta ; Fujisawa, Kazunori ; Wang, Xuyang ; Iyiola, Oluwagbenga Oare ; Perea Lopez, Nestor ; Elias Arriaga, Ana Laura ; Pulickal Rajukumar, Lakshmy ; Zhou, Chanjing ; Kabius, Bernd C. ; Alem, Nasim ; Endo, Morinobu ; Lv, Ruitao ; Mendoza-Cortes, Jose L. ; Terrones Maldonado, Mauricio. / Low-temperature Synthesis of Heterostructures of Transition Metal Dichalcogenide Alloys (WxMo1-xS2) and Graphene with Superior Catalytic Performance for Hydrogen Evolution. In: ACS Nano. 2017 ; Vol. 11, No. 5. pp. 5103-5112.
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abstract = "Large-area (∼cm2) films of vertical heterostructures formed by alternating graphene and transition-metal dichalcogenide (TMD) alloys are obtained by wet chemical routes followed by a thermal treatment at low temperature. In particular, we synthesized stacked graphene and WxMo1-xS2 alloy phases that were used as hydrogen evolution catalysts. We observed a Tafel slope of 38.7 mV dec-1 and 96 mV onset potential (at current density of 10 mA cm-2) when the heterostructure alloy was annealed at 300 °C. These results indicate that heterostructures formed by graphene and W0.4Mo0.6S2 alloys are far more efficient than WS2 and MoS2 by at least a factor of 2, and they are superior compared to other reported TMD systems. This strategy offers a cheap and low temperature synthesis alternative able to replace Pt in the hydrogen evolution reaction (HER). Furthermore, the catalytic activity of the alloy is stable over time, i.e., the catalytic activity does not experience a significant change even after 1000 cycles. Using density functional theory calculations, we found that this enhanced hydrogen evolution in the WxMo1-xS2 alloys is mainly due to the lower energy barrier created by a favorable overlap of the d-orbitals from the transition metals and the s-orbitals of H2; with the lowest energy barrier occurring for the W0.4Mo0.6S2 alloy. Thus, it is now possible to further improve the performance of the {"}inert{"} TMD basal plane via metal alloying, in addition to the previously reported strategies such as creation of point defects, vacancies and edges. The synthesis of graphene/W0.4Mo0.6S2 produced at relatively low temperatures is scalable and could be used as an effective low cost Pt-free catalyst.",
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Low-temperature Synthesis of Heterostructures of Transition Metal Dichalcogenide Alloys (WxMo1-xS2) and Graphene with Superior Catalytic Performance for Hydrogen Evolution. / Lei, Yu; Pakhira, Srimanta; Fujisawa, Kazunori; Wang, Xuyang; Iyiola, Oluwagbenga Oare; Perea Lopez, Nestor; Elias Arriaga, Ana Laura; Pulickal Rajukumar, Lakshmy; Zhou, Chanjing; Kabius, Bernd C.; Alem, Nasim; Endo, Morinobu; Lv, Ruitao; Mendoza-Cortes, Jose L.; Terrones Maldonado, Mauricio.

In: ACS Nano, Vol. 11, No. 5, 23.05.2017, p. 5103-5112.

Research output: Contribution to journalArticle

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T1 - Low-temperature Synthesis of Heterostructures of Transition Metal Dichalcogenide Alloys (WxMo1-xS2) and Graphene with Superior Catalytic Performance for Hydrogen Evolution

AU - Lei, Yu

AU - Pakhira, Srimanta

AU - Fujisawa, Kazunori

AU - Wang, Xuyang

AU - Iyiola, Oluwagbenga Oare

AU - Perea Lopez, Nestor

AU - Elias Arriaga, Ana Laura

AU - Pulickal Rajukumar, Lakshmy

AU - Zhou, Chanjing

AU - Kabius, Bernd C.

AU - Alem, Nasim

AU - Endo, Morinobu

AU - Lv, Ruitao

AU - Mendoza-Cortes, Jose L.

AU - Terrones Maldonado, Mauricio

PY - 2017/5/23

Y1 - 2017/5/23

N2 - Large-area (∼cm2) films of vertical heterostructures formed by alternating graphene and transition-metal dichalcogenide (TMD) alloys are obtained by wet chemical routes followed by a thermal treatment at low temperature. In particular, we synthesized stacked graphene and WxMo1-xS2 alloy phases that were used as hydrogen evolution catalysts. We observed a Tafel slope of 38.7 mV dec-1 and 96 mV onset potential (at current density of 10 mA cm-2) when the heterostructure alloy was annealed at 300 °C. These results indicate that heterostructures formed by graphene and W0.4Mo0.6S2 alloys are far more efficient than WS2 and MoS2 by at least a factor of 2, and they are superior compared to other reported TMD systems. This strategy offers a cheap and low temperature synthesis alternative able to replace Pt in the hydrogen evolution reaction (HER). Furthermore, the catalytic activity of the alloy is stable over time, i.e., the catalytic activity does not experience a significant change even after 1000 cycles. Using density functional theory calculations, we found that this enhanced hydrogen evolution in the WxMo1-xS2 alloys is mainly due to the lower energy barrier created by a favorable overlap of the d-orbitals from the transition metals and the s-orbitals of H2; with the lowest energy barrier occurring for the W0.4Mo0.6S2 alloy. Thus, it is now possible to further improve the performance of the "inert" TMD basal plane via metal alloying, in addition to the previously reported strategies such as creation of point defects, vacancies and edges. The synthesis of graphene/W0.4Mo0.6S2 produced at relatively low temperatures is scalable and could be used as an effective low cost Pt-free catalyst.

AB - Large-area (∼cm2) films of vertical heterostructures formed by alternating graphene and transition-metal dichalcogenide (TMD) alloys are obtained by wet chemical routes followed by a thermal treatment at low temperature. In particular, we synthesized stacked graphene and WxMo1-xS2 alloy phases that were used as hydrogen evolution catalysts. We observed a Tafel slope of 38.7 mV dec-1 and 96 mV onset potential (at current density of 10 mA cm-2) when the heterostructure alloy was annealed at 300 °C. These results indicate that heterostructures formed by graphene and W0.4Mo0.6S2 alloys are far more efficient than WS2 and MoS2 by at least a factor of 2, and they are superior compared to other reported TMD systems. This strategy offers a cheap and low temperature synthesis alternative able to replace Pt in the hydrogen evolution reaction (HER). Furthermore, the catalytic activity of the alloy is stable over time, i.e., the catalytic activity does not experience a significant change even after 1000 cycles. Using density functional theory calculations, we found that this enhanced hydrogen evolution in the WxMo1-xS2 alloys is mainly due to the lower energy barrier created by a favorable overlap of the d-orbitals from the transition metals and the s-orbitals of H2; with the lowest energy barrier occurring for the W0.4Mo0.6S2 alloy. Thus, it is now possible to further improve the performance of the "inert" TMD basal plane via metal alloying, in addition to the previously reported strategies such as creation of point defects, vacancies and edges. The synthesis of graphene/W0.4Mo0.6S2 produced at relatively low temperatures is scalable and could be used as an effective low cost Pt-free catalyst.

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