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Copper-Intercalated Birnessite as a Water Oxidation Catalyst.

Akila C Thenuwara1,2, Samantha L Shumlas1,2, Nuwan H Attanayake1,2

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Intercalating copper into birnessite significantly enhances its water oxidation catalytic activity and stability. This method improves conductivity and shifts electronic properties, crucial for efficient electrocatalysis.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Birnessite, a layered manganese oxide, shows potential for water oxidation but requires activity enhancement.
  • Improving the electrocatalytic performance of birnessite is crucial for applications in energy conversion.

Purpose of the Study:

  • To develop a synthetic method for increasing birnessite's catalytic activity for water oxidation.
  • To investigate the effect of copper intercalation on birnessite's electrochemical properties and stability.

Main Methods:

  • Copper intercalation into birnessite using a Cu(+)-bearing precursor.
  • Characterization using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Inductively Coupled Plasma (ICP), and Raman spectroscopy.
  • Electrocatalytic studies including overpotential and Tafel slope measurements, impedance spectroscopy, and density functional theory (DFT) calculations.

Main Results:

  • Cu-modified birnessite exhibited a lower overpotential (∼490 mV) and Tafel slope (126 mV/decade) for water oxidation compared to unmodified birnessite (∼700 mV, 240 mV/decade).
  • Impedance spectroscopy revealed lower charge transfer resistivity in Cu-modified birnessite, indicating enhanced conductivity.
  • DFT calculations suggested a semiconductor-to-metallic transition upon Cu(0) intercalation, supported by experimental findings.
  • Cu-modified birnessite demonstrated increased stability, lasting approximately three times longer under working conditions.

Conclusions:

  • Intercalation of copper, particularly Cu(0), significantly enhances the catalytic activity and stability of birnessite for water oxidation.
  • The enhanced performance is attributed to increased conductivity and altered electronic properties resulting from copper intercalation.
  • The synthetic method provides a viable route for developing advanced electrocatalysts for water oxidation.