An electrochemical approach is developed that allows for the control of both proton and electron transfer rates in the O 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.

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.

The electrolysis of water is limited by the high overpotential of the oxygen evolution reaction (OER). In search of an inexpensive and efficient catalyst for OER, we construct electrocatalysts using cuprous oxide (Cu 2 O) thin films modified with a Ni overlayer. By tuning the amount of Ni electrodeposited on top of the Cu 2 O, we determine the optimal ratio of Ni/Cu 2 O for OER in alkaline solution with the best catalyst possessing an onset overpotential of only 150 mV. Surface characterization using XRD, SEM, EDS, and AFM indicates that the composition and morphology of the catalyst is highly dependent upon the amount of Ni electrodeposited, and these differences determine catalyst performance. In particular, the optimal catalyst contains a fairly uniform distribution of Ni and Cu 2 O particles, suggesting that bimetallic sites facilitate efficient O 2 evolution.