Uncovering Interfacial Oxygen-Bridged Binuclear Metal Centers of Heterogenized Molecular Catalyst for Water...

The success of different heterogeneous strategies of organometallic catalysts has been demonstrated to achieve high selectivity and activity in photo/electrocatalysis. However, yielding their catalytic mechanisms at complex molecule-electrode and electrochemical interfaces remains a great challenge. Herein, shell-isolated nanoparticle-enhanced Raman spectroscopy is employed to elucidate the dynamic process, interfacial structure, and intermediates of copper hydroxide-2-2' bipyridine on Au electrode ((bpy)Cu(OH)₂/Au) during the oxygen evolution reaction (OER). Direct Raman molecular evidences reveal that the interfacial (bpy)Cu(OH)₂ oxidizes into Cu(III) and bridges to Au atoms via oxygenated species, forming (bpy)Cu(III)O₂-Au with oxygen-bridged binuclear metal centers of Cu(III)-O-Au for the OER. As the potential further increases, Cu(III)-O-Au combines with surface hydroxyl groups (*OH) to form the important intermediate of Cu(III)-OOH-Au, which then turns into Cu(III)-OO-Au to release O₂. Furthermore, in situ electrochemical impedance spectroscopy proves that the Cu(III)-O-Au has lower resistance and faster mass transport of hydroxy to enhance OER. Theoretical calculations reveal that the formation of Cu(III)-O-Au significantly modify the elementary reaction steps of the OER, resulting in a lower potential-determining step of ≈0.58 V than that of bare Au. This work provides new insights into the OER mechanism of immobilized-molecule catalysts for the development and application of renewable energy conversion devices.