Melamine-Based Hydrogen-bonded Systems as Organoelectrocatalysts for Water Oxidation Reaction

Applications of small organic molecules and hydrogen-bonded aggregates, instead of traditional transition-metal-based electrocatalysts, are gaining momentum for addressing the issue of low-cost generation of H₂ to power a sustainable environment. Such systems offer the possibility to integrate desired functional moieties with predictive structural repetition for modulating their properties. Despite these advantages, hydrogen-bonded organic systems have largely remained unexplored, especially as electrocatalysts. Melamine and adipic acid-based hydrogen-bonded organic ionic (BMA) and co-crystal systems developed under varying temperatures are explored as electrocatalysts for water oxidation reaction (WOR). These systems are easily modifiable with precisely designed molecular architecture and judiciously positioned nitrogen atoms. Combined effect of charge-assisted hydrogen bonding stabilizes the ionic BMA system under corrosive alkaline conditions and augments its remarkable electrocatalytic WOR activity, achieving a current density of 10 mA cm^-2 at an overpotential of 387 mV and Faradaic efficiency ∼94.5 %. The enhanced electrocatalytic ability of BMA is attributed to its hydrophilic nature, unique molecular composition with complementary hydrogen-bonded motifs and a high density of positively charged nitrogen atoms on the surface, that facilitates electrostatic interactions and accelerate charge and mass transport processes culminating in a turnover frequency of ∼0.024 s^-1 . This work validates the potential of hydrogen-bonded molecular organo-electrocatalysts towards WOR.