The electrochemical reduction of dioxygen and hydrogen peroxide by molecular copper catalysts

Langerman, M. (2021)

Doctoral Thesis

The electrochemical oxygen reduction reaction (ORR) is an essential half-reaction for the utilization of hydrogen as a sustainable fuel, via the conversion of hydrogen to electrons and protons facilitated by the ORR. In the most common fuel cells, the ORR is requires high loadings of non-abundant platinum based catalysts. Inspired by Laccase, a multicopper oxidase able to perform the ORR at a low overpotential, copper complexes have become interesting targets as non-precious metal catalysts for the ORR.

In this thesis, the ORR performance of molecular copper catalysts and the involved catalytic mechanisms have been investigated. The previously undetermined electrocatalytic mechanism for the ORR by the Cu(tmpa) copper complex was elucidated. Hydrogen peroxide was shown to play an important role in the catalytic cycle as a reaction intermediate. This has interesting implications for the sustainable electrochemical production of hydrogen peroxide. Furthermore, the reduction of hydrogen peroxide shows striking similarities with Fenton-like reactions observed in copper containing enzymes. Finally, the performance of several different copper electrocatalysts for the reduction of oxygen and hydrogen peroxide was investigated and compared.

• Copper
• Oxygen Reduction
• Hydrogen peroxide
• Electrocatalysis
• Electrochemistry
• Homogenous catalysis
• Coordination chemistry

• All authors: Langerman, M.
• Supervisor: Hetterscheid, D.G.H.; Bouwman, E.
• Committee: Overkleeft, H.S.; Koper, M.T.M.; Bonnet, S.A.; Mayer, J.; Marinescu, S.C.
• Qualification: Doctor (dr.)
• Awarding Institution: Leiden Institute of Chemistry (LIC), Faculty of Science, Leiden University
• Date: 2021-10-12
• ISBN (print): 9789464214871