4.8 Article

Selective anodes for seawater splitting via functionalization of manganese oxides by a plasma-assisted process

Journal

APPLIED CATALYSIS B-ENVIRONMENTAL
Volume 284, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apcatb.2020.119684

Keywords

Manganese oxides; Plasma enhanced-chemical vapor deposition; Sputtering; Oxygen evolution reaction; Seawater splitting

Funding

  1. Padova University (DOR 2017-2020)
  2. Padova University (P-DiSC) [03BIRD2018]
  3. INSTM Consortium [INSTMPD004]
  4. AMGA Foundation (Mn4Energy project)
  5. Hercules fund from the Flemish Government
  6. GOA project 'Solarpaint' (University of Antwerp)
  7. EU-H2020 programme [823717]
  8. Generalitat de Catalunya through the CERCA Programme, M2E [2017SGR1246]
  9. ERDEF-MINECO coordinated projects [ENE2017-85087-C3, ENE2016-80788-C5-5-R]

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Through a specific material combination, selective triggering of oxygen generation and reduction of chlorine production in seawater has been achieved. The combination of MnO2 and Co3O4 performs the best in alkaline seawater splitting, showing significant results.
The electrolysis of seawater, a significantly more abundant natural reservoir than freshwater, stands as a promising alternative for sustainable hydrogen production, provided that the competitive chloride electro-oxidation is minimized. Herein, we propose an original material combination to selectively trigger oxygen evolution from seawater at expenses of chlorine generation. The target systems, based on MnO2 or Mn2O3 decorated with Fe2O3 or Co3O4, are fabricated by plasma enhanced-chemical vapor deposition of manganese oxides, functionalization with Fe2O3 and Co3O4 by sputtering, and annealing in air/Ar to obtain Mn(IV)/Mn(III) oxides. Among the various options, MnO2 decorated with Co3O4 yields the best performances in alkaline seawater splitting, with an outstanding Tafel slope of approximate to 40 mV x dec(-1) and an overpotential of 450 mV, enabling to rule out chlorine evolution. These attractive performances, resulting from the synergistic contribution of catalytic and electronic effects, open the door to low-cost hydrogen generation from seawater under real-world conditions, paving the way to eventual large-scale applications.

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