Linker modulated peroxide electrosynthesis using metal-organic nanosheets

The electrochemical synthesis of hydrogen peroxide (H2O2), a widely used oxidant, is emerging as a green alternative to the conventional anthraquinone method. In this work, Ni-based metal-organic nanosheet (Ni-MONs) catalysts constructed using a variety of linkers were studied as oxygen reduction catalysts. Using a host of analytical techniques, we reveal how modulating the terephthalic acid linker with hydroxy, amine, and fluorine groups impacts the resulting physical and electronic structure of the Ni catalytic sites. These changes further impact the selectivity for H2O2, with the Ni-Amine-MON reaching near 100% Faradaic efficiency at minimal overpotential for the 2e- H2O2 pathway in alkaline electrolyte. Finally, we translate the Ni-Amine-MON catalyst to a gas-diffusion reaction geometry and demonstrate a H2O2 partial current density of 200 mA/cm2 while maintaining 85% Faradaic efficiency. In all, this study puts forth a simple route to catalyst modulation for highly effective H2O2 electrosynthesis.