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Surface galvanic formation of Co-OH on Birnessite and its catalytic activity for the oxygen evolution reaction

Surface galvanic formation of Co-OH on Birnessite and its catalytic activity for the oxygen evolution reaction
Surface galvanic formation of Co-OH on Birnessite and its catalytic activity for the oxygen evolution reaction
Low cost, high-efficient catalysts for water splitting can be potentially fulfilled by developing earth abundant metal oxides. In this work, surface galvanic formation of Co-OH on K0.45MnO2 (KMO) was achieved via the redox reaction of hydrated Co2+ with crystalline Mn4+. The synthesis method takes place at ambient temperature without using any surfactant agent or organic solvent, providing a clean, green route for the design of highly efficient catalysts. The redox reaction resulted in the formation of ultrathin Co-OH nanoflakes with high electrochemical surface area. X-ray adsorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the changes in the oxidation state of the bulk and surface species on the Co-OH nanoflakes supported on the KMO. The effect of the anions, chloride, nitrate and sulfate, on the preparation of the catalyst was evaluated by electrochemical and spectrochemical means. XPS and Time of flight secondary ion mass spectrometry (ToF-SIMS) analysis demonstrated that the layer of CoOxHy deposited on the KMO and its electronic structure strongly depends on the anion of the precursor used during the synthesis of the catalyst. In particular, it was found that Cl favors the formation of Co-OH, changing the rate determining step of the reaction, which enhances the catalytic activity towards the OER, producing the most active OER catalyst in alkaline media.
oxygen evolution reaction, surface galvanic synthesis, layered manganese oxide, anion effect
0021-9517
304-314
Pu, Yayun
e0db849a-bc5e-4ff6-9dae-58d0759da4dc
Celorrio, Veronica
5ebb7fb5-a74c-4872-9795-5830dc915d0b
Stockmann, Jöerg M.
2465f415-746c-43ff-82b6-31530852756f
Sobol, Oded
368d32c0-e01e-469c-86a5-7e1461252caf
Sun, Zongzhao
b05b2f0d-cfa2-4737-a0ce-f27c71681477
Wang, Wu
a42d9b38-79b3-4d60-834b-ab29ba4dec79
Lawrence, Matthew J.
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Radnik, Jörg
c712123f-7310-4560-a131-760a669ad1a9
Russell, Andrea E.
b6b7c748-efc1-4d5d-8a7a-8e4b69396169
Hodoroaba, Vasile-Dan
f48865c1-35c3-4511-b747-e0f19613b971
Huang, Limin
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Rodriguez, Paramaconi
5a751a4e-490e-42bb-9c22-7b0fc72e9a09
Pu, Yayun
e0db849a-bc5e-4ff6-9dae-58d0759da4dc
Celorrio, Veronica
5ebb7fb5-a74c-4872-9795-5830dc915d0b
Stockmann, Jöerg M.
2465f415-746c-43ff-82b6-31530852756f
Sobol, Oded
368d32c0-e01e-469c-86a5-7e1461252caf
Sun, Zongzhao
b05b2f0d-cfa2-4737-a0ce-f27c71681477
Wang, Wu
a42d9b38-79b3-4d60-834b-ab29ba4dec79
Lawrence, Matthew J.
76aef46e-f0d8-4af4-8fa0-0bf4219d8956
Radnik, Jörg
c712123f-7310-4560-a131-760a669ad1a9
Russell, Andrea E.
b6b7c748-efc1-4d5d-8a7a-8e4b69396169
Hodoroaba, Vasile-Dan
f48865c1-35c3-4511-b747-e0f19613b971
Huang, Limin
9e9bdb52-baa7-427a-9086-4fafbd9c785a
Rodriguez, Paramaconi
5a751a4e-490e-42bb-9c22-7b0fc72e9a09

Pu, Yayun, Celorrio, Veronica, Stockmann, Jöerg M., Sobol, Oded, Sun, Zongzhao, Wang, Wu, Lawrence, Matthew J., Radnik, Jörg, Russell, Andrea E., Hodoroaba, Vasile-Dan, Huang, Limin and Rodriguez, Paramaconi (2021) Surface galvanic formation of Co-OH on Birnessite and its catalytic activity for the oxygen evolution reaction. Journal of Catalysis, 396, 304-314. (doi:10.1016/j.jcat.2021.02.025).

Record type: Article

Abstract

Low cost, high-efficient catalysts for water splitting can be potentially fulfilled by developing earth abundant metal oxides. In this work, surface galvanic formation of Co-OH on K0.45MnO2 (KMO) was achieved via the redox reaction of hydrated Co2+ with crystalline Mn4+. The synthesis method takes place at ambient temperature without using any surfactant agent or organic solvent, providing a clean, green route for the design of highly efficient catalysts. The redox reaction resulted in the formation of ultrathin Co-OH nanoflakes with high electrochemical surface area. X-ray adsorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the changes in the oxidation state of the bulk and surface species on the Co-OH nanoflakes supported on the KMO. The effect of the anions, chloride, nitrate and sulfate, on the preparation of the catalyst was evaluated by electrochemical and spectrochemical means. XPS and Time of flight secondary ion mass spectrometry (ToF-SIMS) analysis demonstrated that the layer of CoOxHy deposited on the KMO and its electronic structure strongly depends on the anion of the precursor used during the synthesis of the catalyst. In particular, it was found that Cl favors the formation of Co-OH, changing the rate determining step of the reaction, which enhances the catalytic activity towards the OER, producing the most active OER catalyst in alkaline media.

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Accepted/In Press date: 19 February 2021
e-pub ahead of print date: 5 March 2021
Published date: 1 April 2021
Keywords: oxygen evolution reaction, surface galvanic synthesis, layered manganese oxide, anion effect

Identifiers

Local EPrints ID: 447120
URI: http://eprints.soton.ac.uk/id/eprint/447120
ISSN: 0021-9517
PURE UUID: 5d1a61e7-f317-4bbb-95f7-28ab61ae2131
ORCID for Andrea E. Russell: ORCID iD orcid.org/0000-0002-8382-6443

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Date deposited: 03 Mar 2021 17:32
Last modified: 18 May 2022 04:01

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Contributors

Author: Yayun Pu
Author: Veronica Celorrio
Author: Jöerg M. Stockmann
Author: Oded Sobol
Author: Zongzhao Sun
Author: Wu Wang
Author: Matthew J. Lawrence
Author: Jörg Radnik
Author: Vasile-Dan Hodoroaba
Author: Limin Huang
Author: Paramaconi Rodriguez

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