Effect of Partial Replacement of Pt-Based Catalysts with Fe- and Co-for Oxygen Evolution Reaction in Pem Water Electrolysis: A Combined Theoretical and Experimental Study

Antonia Stoyanova; Mazharul M. Islam; Galin Borisov; Thomas Bredow; Elefteria Lefterova; Evelina Slavcheva

Antonia Stoyanova Institute of Electrochemistry and Energy Systems BAS, 10 G. Bonchev Str., BG-1113 Sofia.
Mazharul M. Islam Mulliken Center for Theoretical Chemistry, Institute of Physical and Theoretical Chemistry, University of Bonn, Beringstra 46, 53115 Bonn, Germany.
Galin Borisov Institute of Electrochemistry and Energy Systems BAS, 10 G. Bonchev Str., BG-1113 Sofia.
Thomas Bredow Mulliken Center for Theoretical Chemistry, Institute of Physical and Theoretical Chemistry, University of Bonn, Beringstrae 46, 53115 Bonn, Germany.
Elefteria Lefterova Institute of Electrochemistry and Energy Systems BAS, 10 G. Bonchev Str., BG-1113 Sofia.
Evelina Slavcheva Institute of Electrochemistry and Energy Systems BAS, 10 G. Bonchev Str., BG-1113 Sofia.

Keywords: PEM Water Electrolysis, Quantum-Chemical Calculations, Density Functional Theory, Adsorption and Co-Adsorption, Pt-Based Binary Compounds, Titanium Dioxide.

Abstract

The adsorption of Pt_n (n = 1−4) clusters and co-adsorption of Pt_n-Co and Pt_n-Fe on the defect-free anatase TiO₂(101) surface have been studied theoretically at density functional theory (DFT) level. The most stable configurations are observed due to Pt₂ and Pt₃-clusters adsorbed on the titania surface. The electronic structure analyses show that the Fermi level is pinned by Pt, which reduces the band gap from ~3 eV of the clean surface to significantly less than 1 eV for Pt₃. For the co-adsorption of Fe-Pt and Co-Pt, there is a strong bond formation of Fe and Co with the surface O and Ti atoms. In both cases, Fe and Co stay far away from the Pt atom. Due to strong interaction of adsorbed elements with Ti, the co-adsorption energy is larger than the corresponding Pt₃ adsorption energy. The higher stability of the co-adsorption of Fe-Pt_n compared to the Co-Pt_n is in agreement with the electrochemical experimental results which confirm that Fe-containing catalysts deposited on titanium dioxide support (Ebonex) will be higher efficient than Co-containing ones toward oxygen evolution in proton-exchange membrane water electrolysis. The observed effect can be explained with formation of solid solution between the metallic components and a realization of synergetic effect.

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