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Highly active copper‐based electrocatalyst for water oxidation at neutral pH

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Show simple item record Zhang, Shiguo Younus, Hussein A. Zhang, Yan Vandichel, Matthias Ahmad, Nazir Laasonen, Kari Verpoort, Francis Zhang, Ce 2020-08-05T12:59:05Z 2020
dc.description peer-reviewed en_US
dc.description The full text of this article will not be available in ULIR until the embargo expires on the 15/07/2021
dc.description.abstract The sluggish kinetics of the oxygen evolution reaction at the anode severely limits the hydrogen production at the cathode in water spitting systems. While electrocatalytic systems based on cheap and earth-abundant metal copper catalysts have been promising for water oxidation under basic conditions, only very few examples with high overpotential can be operated under acidic or neutral conditions, even though hydrogen evolution in the latter case is much easier. This work presents an efficient and robust Cu-based molecular catalyst, which self-assembles as a periodic film from its precursors under aqueous conditions on the surface of glassy carbon electrodes (GCE). This film catalyzes the oxygen evolution reaction (OER) under neutral conditions with impressively low overpotential. In controlled potential electrolysis, a stable catalytic current of 1.0 mA/cm2 can be achieved at only 2.0 V (vs. RHE) and no remarkable decrease in the catalytic current is observed even after prolonged bulk electrolysis. The catalyst displays first-order kinetics and a single site mechanism for water oxidation with a TOF (kcat) of 0.6 s-1. DFT calculations are performed to study the OER behavior of the periodic Cu(TCA)2 (HTCA = 1-mesityl-1H-1,2,3-triazole-4 carboxylic acid) film and reveal that TCA defects within the film create Cu(I) active sites which can provide a low overpotential route for OER. This route involves Cu(I), Cu(II)-OH, Cu(III)=O and Cu(II)-OOH intermediates and is enabled at a potential of 1.54 V (vs. RHE), requiring an overpotential of 0.31 V. This corresponds well with an overpotential of ~ 0.29 V obtained experimentally for the grown catalytic film after 100 CV cycles at pH=6. However, to reach a higher current density of 1 mA cm−2, an overpotential of 0.72 V is required. en_US
dc.language.iso eng en_US
dc.publisher Wiley and Sons Ltd en_US
dc.relation.ispartofseries ChemSusChem; 13 (18), pp. 5088-5099
dc.rights "This is the peer reviewed author version of the following article:Highly active copper‐based electrocatalyst for water oxidation at neutral pH, which has been published in final form at . This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. en_US
dc.subject electrochemical water oxidation en_US
dc.subject molecular catalyst en_US
dc.subject Cu metal-organic-material en_US
dc.subject neutral conditions en_US
dc.subject DFT calculations en_US
dc.title Highly active copper‐based electrocatalyst for water oxidation at neutral pH en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US
dc.identifier.doi 10.1002/cssc.202001444
dc.contributor.sponsor National Natural Science Foundation of China en_US
dc.contributor.sponsor Outstanding Youth Scientist Foundation of Hunan Province en_US
dc.contributor.sponsor Youth 1000 Talent Program of China, the Science and Technology Innovation Platform and Talent Plan of Hunan Province en_US
dc.relation.projectid 21872046 en_US
dc.relation.projectid 51772089 en_US
dc.relation.projectid 2018JJ1009 en_US
dc.relation.projectid 2017XK2023 en_US
dc.relation.projectid 2019GK2235 en_US 2021-07-15
dc.embargo.terms 2021-07-15 en_US
dc.rights.accessrights info:eu-repo/semantics/embargoedAccess en_US

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