In situ electrochemically synthesized Pt-MoO3−x nanostructure catalysts for efficient hydrogen evolution reaction

Daewon Lee; Youngmin Kim; Hyun Woo Kim; Min Choi; Noejung Park; Hyunju Chang; Youngkook Kwon; Jong Hyeok Park; Hyung Ju Kim

doi:10.1016/j.jcat.2019.10.027

In situ electrochemically synthesized Pt-MoO_3−x nanostructure catalysts for efficient hydrogen evolution reaction

Daewon Lee, Youngmin Kim, Hyun Woo Kim, Min Choi, Noejung Park, Hyunju Chang, Youngkook Kwon, Jong Hyeok Park, Hyung Ju Kim

Department of Chemical and Biomolecular Engineering

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

31 Citations (Scopus)

Abstract

Designing and preparing highly active and stable nanostructured Pt-based catalysts with ultralow Pt loading are still challenging for electrochemical applications such as water electrolysis and fuel cells. Here we report for the first time an in situ electrochemical process to synthesize Pt-MoO_3−x nanoflakes (NFs) overgrown on commercial bulk MoS₂ by employing a facile and simple electrochemical method without using any expensive precious metal salts. The overgrowth of Pt-MoO_3−x NFs on the bulk MoS₂ surface is conducted by applying electrical energy to the bulk MoS₂ and using Pt counter electrode dissolution in an acidic solution. In spite of their 10 times lower Pt loadings compared to commercial Pt black (Alfa Aesar), the synthesized Pt-MoO_3−x NFs demonstrate excellent catalytic performance with a Pt mass activity of 2.83 A/mg_Pt at the overpotential of 100 mV for electrochemical hydrogen evolution reaction (HER), an approximately 4 times higher value than the value of 0.76 A/mg_Pt at the overpotential of 100 mV for commercial Pt black. We hypothesize that the outstanding HER characteristics of Pt-MoO_3−x NFs are related to the existence and increase of Pt-MoO₃ interfacial sites and oxygen vacancy sites such as Mo⁵⁺ in the Pt-MoO_3−x NF structures. In addition, our density functional theory (DFT) calculations demonstrate that Pt and O sites at Pt and MoO₃ interfaces and O sites at defective MoO_3−x in the Pt-MoO_3−x NFs contribute to accelerate the HER.

Original language	English
Pages (from-to)	1-13
Number of pages	13
Journal	Journal of Catalysis
Volume	381
DOIs	https://doi.org/10.1016/j.jcat.2019.10.027
Publication status	Published - 2020 Jan

Bibliographical note

Funding Information:
The authors very much appreciate Prof. George W. Huber (Department of Chemical and Biological Engineering, University of Wisconsin-Madison) for valuable comments and constructive discussion to improve this manuscript. We also thank Mr. Hyung Bin Bae from the KAIST Analysis Center for Research Advancement (KARA) for the HAADF-STEM imaging and EDS elemental mapping analyses. This work was supported by the core KRICT project (grant numbers: SI1911-50 and KK1963-402 ) from the Korea Research Institute of Chemical Technology. Appendix A

Funding Information:
The authors very much appreciate Prof. George W. Huber (Department of Chemical and Biological Engineering, University of Wisconsin-Madison) for valuable comments and constructive discussion to improve this manuscript. We also thank Mr. Hyung Bin Bae from the KAIST Analysis Center for Research Advancement (KARA) for the HAADF-STEM imaging and EDS elemental mapping analyses. This work was supported by the core KRICT project (grant numbers: SI1911-50 and KK1963-402) from the Korea Research Institute of Chemical Technology.

Publisher Copyright:
© 2019 Elsevier Inc.

All Science Journal Classification (ASJC) codes

Catalysis
Physical and Theoretical Chemistry

Access to Document

10.1016/j.jcat.2019.10.027

Cite this

@article{241ca019e4d843689b08d8d561222603,

title = "In situ electrochemically synthesized Pt-MoO3−x nanostructure catalysts for efficient hydrogen evolution reaction",

abstract = "Designing and preparing highly active and stable nanostructured Pt-based catalysts with ultralow Pt loading are still challenging for electrochemical applications such as water electrolysis and fuel cells. Here we report for the first time an in situ electrochemical process to synthesize Pt-MoO3−x nanoflakes (NFs) overgrown on commercial bulk MoS2 by employing a facile and simple electrochemical method without using any expensive precious metal salts. The overgrowth of Pt-MoO3−x NFs on the bulk MoS2 surface is conducted by applying electrical energy to the bulk MoS2 and using Pt counter electrode dissolution in an acidic solution. In spite of their 10 times lower Pt loadings compared to commercial Pt black (Alfa Aesar), the synthesized Pt-MoO3−x NFs demonstrate excellent catalytic performance with a Pt mass activity of 2.83 A/mgPt at the overpotential of 100 mV for electrochemical hydrogen evolution reaction (HER), an approximately 4 times higher value than the value of 0.76 A/mgPt at the overpotential of 100 mV for commercial Pt black. We hypothesize that the outstanding HER characteristics of Pt-MoO3−x NFs are related to the existence and increase of Pt-MoO3 interfacial sites and oxygen vacancy sites such as Mo5+ in the Pt-MoO3−x NF structures. In addition, our density functional theory (DFT) calculations demonstrate that Pt and O sites at Pt and MoO3 interfaces and O sites at defective MoO3−x in the Pt-MoO3−x NFs contribute to accelerate the HER.",

author = "Daewon Lee and Youngmin Kim and Kim, {Hyun Woo} and Min Choi and Noejung Park and Hyunju Chang and Youngkook Kwon and Park, {Jong Hyeok} and Kim, {Hyung Ju}",

note = "Funding Information: The authors very much appreciate Prof. George W. Huber (Department of Chemical and Biological Engineering, University of Wisconsin-Madison) for valuable comments and constructive discussion to improve this manuscript. We also thank Mr. Hyung Bin Bae from the KAIST Analysis Center for Research Advancement (KARA) for the HAADF-STEM imaging and EDS elemental mapping analyses. This work was supported by the core KRICT project (grant numbers: SI1911-50 and KK1963-402 ) from the Korea Research Institute of Chemical Technology. Appendix A Funding Information: The authors very much appreciate Prof. George W. Huber (Department of Chemical and Biological Engineering, University of Wisconsin-Madison) for valuable comments and constructive discussion to improve this manuscript. We also thank Mr. Hyung Bin Bae from the KAIST Analysis Center for Research Advancement (KARA) for the HAADF-STEM imaging and EDS elemental mapping analyses. This work was supported by the core KRICT project (grant numbers: SI1911-50 and KK1963-402) from the Korea Research Institute of Chemical Technology. Publisher Copyright: {\textcopyright} 2019 Elsevier Inc.",

year = "2020",

month = jan,

doi = "10.1016/j.jcat.2019.10.027",

language = "English",

volume = "381",

pages = "1--13",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

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TY - JOUR

T1 - In situ electrochemically synthesized Pt-MoO3−x nanostructure catalysts for efficient hydrogen evolution reaction

AU - Lee, Daewon

AU - Kim, Youngmin

AU - Kim, Hyun Woo

AU - Choi, Min

AU - Park, Noejung

AU - Chang, Hyunju

AU - Kwon, Youngkook

AU - Park, Jong Hyeok

AU - Kim, Hyung Ju

N1 - Funding Information: The authors very much appreciate Prof. George W. Huber (Department of Chemical and Biological Engineering, University of Wisconsin-Madison) for valuable comments and constructive discussion to improve this manuscript. We also thank Mr. Hyung Bin Bae from the KAIST Analysis Center for Research Advancement (KARA) for the HAADF-STEM imaging and EDS elemental mapping analyses. This work was supported by the core KRICT project (grant numbers: SI1911-50 and KK1963-402 ) from the Korea Research Institute of Chemical Technology. Appendix A Funding Information: The authors very much appreciate Prof. George W. Huber (Department of Chemical and Biological Engineering, University of Wisconsin-Madison) for valuable comments and constructive discussion to improve this manuscript. We also thank Mr. Hyung Bin Bae from the KAIST Analysis Center for Research Advancement (KARA) for the HAADF-STEM imaging and EDS elemental mapping analyses. This work was supported by the core KRICT project (grant numbers: SI1911-50 and KK1963-402) from the Korea Research Institute of Chemical Technology. Publisher Copyright: © 2019 Elsevier Inc.

PY - 2020/1

Y1 - 2020/1

N2 - Designing and preparing highly active and stable nanostructured Pt-based catalysts with ultralow Pt loading are still challenging for electrochemical applications such as water electrolysis and fuel cells. Here we report for the first time an in situ electrochemical process to synthesize Pt-MoO3−x nanoflakes (NFs) overgrown on commercial bulk MoS2 by employing a facile and simple electrochemical method without using any expensive precious metal salts. The overgrowth of Pt-MoO3−x NFs on the bulk MoS2 surface is conducted by applying electrical energy to the bulk MoS2 and using Pt counter electrode dissolution in an acidic solution. In spite of their 10 times lower Pt loadings compared to commercial Pt black (Alfa Aesar), the synthesized Pt-MoO3−x NFs demonstrate excellent catalytic performance with a Pt mass activity of 2.83 A/mgPt at the overpotential of 100 mV for electrochemical hydrogen evolution reaction (HER), an approximately 4 times higher value than the value of 0.76 A/mgPt at the overpotential of 100 mV for commercial Pt black. We hypothesize that the outstanding HER characteristics of Pt-MoO3−x NFs are related to the existence and increase of Pt-MoO3 interfacial sites and oxygen vacancy sites such as Mo5+ in the Pt-MoO3−x NF structures. In addition, our density functional theory (DFT) calculations demonstrate that Pt and O sites at Pt and MoO3 interfaces and O sites at defective MoO3−x in the Pt-MoO3−x NFs contribute to accelerate the HER.

AB - Designing and preparing highly active and stable nanostructured Pt-based catalysts with ultralow Pt loading are still challenging for electrochemical applications such as water electrolysis and fuel cells. Here we report for the first time an in situ electrochemical process to synthesize Pt-MoO3−x nanoflakes (NFs) overgrown on commercial bulk MoS2 by employing a facile and simple electrochemical method without using any expensive precious metal salts. The overgrowth of Pt-MoO3−x NFs on the bulk MoS2 surface is conducted by applying electrical energy to the bulk MoS2 and using Pt counter electrode dissolution in an acidic solution. In spite of their 10 times lower Pt loadings compared to commercial Pt black (Alfa Aesar), the synthesized Pt-MoO3−x NFs demonstrate excellent catalytic performance with a Pt mass activity of 2.83 A/mgPt at the overpotential of 100 mV for electrochemical hydrogen evolution reaction (HER), an approximately 4 times higher value than the value of 0.76 A/mgPt at the overpotential of 100 mV for commercial Pt black. We hypothesize that the outstanding HER characteristics of Pt-MoO3−x NFs are related to the existence and increase of Pt-MoO3 interfacial sites and oxygen vacancy sites such as Mo5+ in the Pt-MoO3−x NF structures. In addition, our density functional theory (DFT) calculations demonstrate that Pt and O sites at Pt and MoO3 interfaces and O sites at defective MoO3−x in the Pt-MoO3−x NFs contribute to accelerate the HER.

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