Conjugated Coordination Polymer Aerogels with Disordered Interfacial Water Structures for Enhanced Electrocatalytic Oxygen Evolution Kinetics

ABSTRACT Beyond rational design of active sites, regulation of the local chemical environment of electrocatalysts to promote the reactant transport dynamics is crucial for enhancing the reaction kinetics, which faces significant limitations owing to the rigid hydrogen‐bond networks formed by interfacial water molecules. Here, an entropy‐derived regulation strategy was proposed to engineer disordered interfacial water structures, which induces a flexible and adaptive environment that can substantially enhance the reactant transport dynamics and reaction kinetics. Taking a conjugated coordination polymer aerogel with homogeneous single‐atom metal active sites as the model system, a comparative study investigating high‐entropy and low‐entropy conjugated coordination polymer aerogels (denoted as HE‐CCPA and LE‐CCPA) was carried out. Our findings reveal that, relative to LE‐CCPA, the inhomogeneity of electron density distribution and reactant adsorption across multiple different single‐atom metal sites of the HE‐CCPA profoundly disrupts the rigid hydrogen‐bond network, resulting in disordered interfacial water structures that can appreciably facilitate the transport dynamics of hydroxide ion reactants to improve the alkaline oxygen evolution kinetics. These findings highlight disordered interfacial water engineering as a promising approach for performance enhancement in widespread aqueous electrocatalysis.