University of Limerick
Browse
Vandichel_2020_Highly.pdf (2.08 MB)

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

Download (2.08 MB)
journal contribution
posted on 2020-08-05, 12:59 authored by Shiguo Zhang, Hussein A. Younus, Yan Zhang, Matthias VandichelMatthias Vandichel, Nazir Ahmad, Kari Laasonen, Francis Verpoort, Ce Zhang
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.

Funding

Two loop calculations in manifestly Lorentz invariant chiral perturbation theory for baryons

Deutsche Forschungsgemeinschaft

Find out more...

History

Publication

ChemSusChem; 13 (18), pp. 5088-5099

Publisher

Wiley and Sons Ltd

Note

peer-reviewed

Other Funding information

National Natural Science Foundation of China, Outstanding Youth Scientist Foundation of Hunan Province, Youth 1000 Talent Program of China, Science and Technology Innovation Platform and Talent Plan of Hunan Province

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 https://doi.org/10.1002/cssc.202001444 . This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. http://olabout.wiley.com/WileyCDA/Section/id-828039.html#terms

Language

English

Usage metrics

    University of Limerick

    Categories

    No categories selected

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC