Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques

Thanh Tran-Phu; Manjunath Chatti; Joshua Leverett; Thi Kim Anh Nguyen; Darcy Simondson; Dijon A. Hoogeveen; Alexander Kiy; The Duong; Bernt Johannessen; Jaydon Meilak; Patrick Kluth; Rose Amal; Alexandr N. Simonov; Rosalie K. Hocking; Rahman Daiyan; Antonio Tricoli

doi:10.1002/smll.202208074

Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co₃O₄ during Water Electrolysis via In Situ Spectroelectrochemical Techniques

Thanh Tran-Phu
, Manjunath Chatti
, Joshua Leverett
, Thi Kim Anh Nguyen
, Darcy Simondson
, Dijon A. Hoogeveen
, Alexander Kiy
, The Duong
, Bernt Johannessen
, Jaydon Meilak
, Patrick Kluth
, Rose Amal
, Alexandr N. Simonov
, Rosalie K. Hocking
, Rahman Daiyan
, Antonio Tricoli

School of Chemistry

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

50 Citations (Scopus)

Abstract

Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H₂) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H₂ production. Here, a scalable strategy to prepare doped cobalt oxide (Co₃O₄) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co₃O₄ electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm⁻² for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g⁻¹ at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co₃O₄ as a low-cost material for green hydrogen electrocatalysis at large scales.

Original language	English
Article number	2208074
Number of pages	11
Journal	Small
Volume	19
Issue number	25
DOIs	https://doi.org/10.1002/smll.202208074
Publication status	Published - 21 Jun 2023

Keywords

bifunctional water electrolysis
in situ Raman
in situ X-ray absorption spectroscopy (XAS)
spinel cobalt oxides
water electrolyzers

Access to Document

10.1002/smll.202208074Licence: CC BY-NC

Cite this

Tran-Phu, T., Chatti, M., Leverett, J., Nguyen, T. K. A., Simondson, D., Hoogeveen, D. A., Kiy, A., Duong, T., Johannessen, B., Meilak, J., Kluth, P., Amal, R., Simonov, A. N., Hocking, R. K., Daiyan, R., & Tricoli, A. (2023). Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co₃O₄ during Water Electrolysis via In Situ Spectroelectrochemical Techniques. Small, 19(25), Article 2208074. https://doi.org/10.1002/smll.202208074

@article{a6bc1eae597a482488672b548edf5c7b,

title = "Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques",

abstract = "Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H2) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H2 production. Here, a scalable strategy to prepare doped cobalt oxide (Co3O4) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co3O4 electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm−2 for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g−1 at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co3O4 as a low-cost material for green hydrogen electrocatalysis at large scales.",

keywords = "bifunctional water electrolysis, in situ Raman, in situ X-ray absorption spectroscopy (XAS), spinel cobalt oxides, water electrolyzers",

author = "Thanh Tran-Phu and Manjunath Chatti and Joshua Leverett and Nguyen, \{Thi Kim Anh\} and Darcy Simondson and Hoogeveen, \{Dijon A.\} and Alexander Kiy and The Duong and Bernt Johannessen and Jaydon Meilak and Patrick Kluth and Rose Amal and Simonov, \{Alexandr N.\} and Hocking, \{Rosalie K.\} and Rahman Daiyan and Antonio Tricoli",

note = "Funding Information: This project was funded by the Australian Renewable Energy Agency (“Renewable Hydrogen for Export” project 2018/RND008 AS008), ARC Training Centre for The Global Hydrogen Economy (IC200100023), and ARC Research Hub on Integrated Energy Storage (IH180100020). A.N.S and A.T. acknowledge ARC for the financial support through Future Fellowships (FT200100317 and FT200100939). R.D. acknowledge ARC for support through Discovery Early Career Researcher Award (DE230101396). The authors also acknowledge the Centre for Advanced Microscopy (CAM) with funding through the Australian Microscopy and Microanalysis Research Facility (AMMRF). Part of this research was undertaken on the XAS and SAXS/WAXS beamlines at the Australian Synchrotron, part of ANSTO, and the authors thank the beamline scientists for their technical assistance. Publisher Copyright: {\textcopyright} 2023 The Authors. Small published by Wiley-VCH GmbH.",

year = "2023",

month = jun,

day = "21",

doi = "10.1002/smll.202208074",

language = "English",

volume = "19",

journal = "Small",

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Tran-Phu, T, Chatti, M, Leverett, J, Nguyen, TKA, Simondson, D, Hoogeveen, DA, Kiy, A, Duong, T, Johannessen, B, Meilak, J, Kluth, P, Amal, R, Simonov, AN, Hocking, RK, Daiyan, R & Tricoli, A 2023, 'Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co₃O₄ during Water Electrolysis via In Situ Spectroelectrochemical Techniques', Small, vol. 19, no. 25, 2208074. https://doi.org/10.1002/smll.202208074

Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co₃O₄ during Water Electrolysis via In Situ Spectroelectrochemical Techniques. / Tran-Phu, Thanh; Chatti, Manjunath; Leverett, Joshua et al.
In: Small, Vol. 19, No. 25, 2208074, 21.06.2023.

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

TY - JOUR

T1 - Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques

AU - Tran-Phu, Thanh

AU - Chatti, Manjunath

AU - Leverett, Joshua

AU - Nguyen, Thi Kim Anh

AU - Simondson, Darcy

AU - Hoogeveen, Dijon A.

AU - Kiy, Alexander

AU - Duong, The

AU - Johannessen, Bernt

AU - Meilak, Jaydon

AU - Kluth, Patrick

AU - Amal, Rose

AU - Simonov, Alexandr N.

AU - Hocking, Rosalie K.

AU - Daiyan, Rahman

AU - Tricoli, Antonio

N1 - Funding Information: This project was funded by the Australian Renewable Energy Agency (“Renewable Hydrogen for Export” project 2018/RND008 AS008), ARC Training Centre for The Global Hydrogen Economy (IC200100023), and ARC Research Hub on Integrated Energy Storage (IH180100020). A.N.S and A.T. acknowledge ARC for the financial support through Future Fellowships (FT200100317 and FT200100939). R.D. acknowledge ARC for support through Discovery Early Career Researcher Award (DE230101396). The authors also acknowledge the Centre for Advanced Microscopy (CAM) with funding through the Australian Microscopy and Microanalysis Research Facility (AMMRF). Part of this research was undertaken on the XAS and SAXS/WAXS beamlines at the Australian Synchrotron, part of ANSTO, and the authors thank the beamline scientists for their technical assistance. Publisher Copyright: © 2023 The Authors. Small published by Wiley-VCH GmbH.

PY - 2023/6/21

Y1 - 2023/6/21

N2 - Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H2) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H2 production. Here, a scalable strategy to prepare doped cobalt oxide (Co3O4) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co3O4 electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm−2 for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g−1 at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co3O4 as a low-cost material for green hydrogen electrocatalysis at large scales.

AB - Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H2) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H2 production. Here, a scalable strategy to prepare doped cobalt oxide (Co3O4) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co3O4 electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm−2 for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g−1 at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co3O4 as a low-cost material for green hydrogen electrocatalysis at large scales.

KW - bifunctional water electrolysis

KW - in situ Raman

KW - in situ X-ray absorption spectroscopy (XAS)

KW - spinel cobalt oxides

KW - water electrolyzers

UR - https://www.scopus.com/pages/publications/85150800733

U2 - 10.1002/smll.202208074

DO - 10.1002/smll.202208074

M3 - Article

AN - SCOPUS:85150800733

SN - 1613-6810

VL - 19

JO - Small

JF - Small

IS - 25

M1 - 2208074

ER -

Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co₃O₄ during Water Electrolysis via In Situ Spectroelectrochemical Techniques

Abstract

Keywords

Access to Document

Other files and links

ARC Training Centre for The Global Hydrogen Economy - UNSW

New dimensions of electrocatalyst design for sustainable energy future

Australian Synchrotron

Cite this

Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques

Abstract

Keywords

Access to Document

Other files and links

Projects

ARC Training Centre for The Global Hydrogen Economy - UNSW

New dimensions of electrocatalyst design for sustainable energy future

Equipment

Australian Synchrotron

Cite this

Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co₃O₄ during Water Electrolysis via In Situ Spectroelectrochemical Techniques