1 research outputs found
Heterogeneous Electrochemical Ammonia Oxidation with a Ru-bda Oligomer Anchored on Graphitic Electrodes via CH−π Interactions
Molecular catalysts can promote ammonia oxidation, providing
mechanistic
insights into the electrochemical N2 cycle for a carbon-free
fuel economy. We report the ammonia oxidation activity of carbon anodes
functionalized with the oligomer {[RuII(bda-κ-N2O2)(4,4′-bpy)]10(4,4′-bpy)}, Rubda-10, where bda is [2,2′-bipyridine]-6,6′-dicarboxylate
and 4,4′-bpy is 4,4′-bipyridine. Electrocatalytic studies
in propylene carbonate demonstrate that the Ru-based hybrid anode
used in a 3-electrode configuration transforms NH3 to N2 and H2 in a 1:3 ratio with near-unity faradaic
efficiency at an applied potential of 0.1 V vs Fc+/0, reaching
turnover numbers of 7500. X-ray absorption spectroscopic analysis
after bulk electrolysis confirms the molecular integrity of the catalyst.
Based on computational studies together with electrochemical evidence,
ammonia nucleophilic attack is proposed as the primary pathway that
leads to critical N–N bond formation