Controlling Proton and Electron Transfer Rates to Enhance the Activity of an Oxygen Reduction Electrocatalyst

An electrochemical approach is developed that allows for the control of both proton and electron transfer rates in the O₂ reduction reaction (ORR). A dinuclear Cu ORR catalyst was prepared that can be covalently attached to thiol‐based self‐assembled monolayers (SAMs) on Au electrodes using azide–alkyne click chemistry. Using this architecture, the electron transfer rate to the catalyst is modulated by changing the length of the SAM, and the proton transfer rate to the catalyst is controlled with an appended lipid membrane modified with proton carriers. By tuning the relative rates of proton and electron transfer, the current density of the lipid‐covered catalyst is enhanced without altering its core molecular structure. This electrochemical platform will help identify optimal thermodynamic and kinetic parameters for ORR catalysts and catalysts of other reactions that involve the transfer of both protons and electrons.