Molecularly Engineered Co-Phthalocyanine Covalent Organic Frameworks for Efficient Nitric Oxide-to-Ammonia Electroreduction

and FE of 82.27%, surpassing its counterparts B-COF and F-COF. Our results constitute the first experimental example of COFs for NORR while outperforming most reported electrocatalysts for this reaction. In situ characterizations and theoretical calculations elucidate that Co sites facilitate adsorption and activation of NO, while pyrrole-N sites synergistically mediate water adsorption and dissociation, establishing a proton-rich microenvironment and accelerating interfacial proton transfer. Our findings provide molecular-level insights into the precise modulation of interactions between NO and catalytic interfaces, accelerating interfacial mass transfer kinetics in the NORR process.