Interface-confined reconstruction of silver Delafossite for ampere-level NH₃ electrosynthesis coupled with plastic...

Developing co-electrolysis technology for electrocatalytic nitrate reduction (NO₃RR) to achieve green ammonia alongside the co-production of value-added chemicals is a promising sustainable strategy. However, the kinetic limitations of NO₃RR and water oxidation present significant economic challenges in industrial conditions. Herein, a strongly coupled heterogeneous interface by encapsulating Ag nanoparticle within an amorphous defect-rich Co₃O_4-x layer is successfully realized via the electrochemical reconstruction of AgCoO₂ precatalysts (R-Ag@Co₃O_4-x). This catalyst exhibits high performance for the ampere-level plasma electrosynthesis of NH₃ and also demonstrates promising application in a zinc-nitrate/glycerol hybrid battery, achieving high charge/discharge efficiency with a maximum power density of 9.83 mW cm^-2. Furthermore, by coupling anodic poly (ethylene terephthalate)-derived ethylene glycol oxidation reaction (EGOR) with NO₃RR, a paired electrolyzer is constructed, achieving NH₃ and formate yields of 100.7 mg h^-1 cm^-2 and 360.77 mg h^-1 cm^-2 at 1 A cm^-2, exceptional long-term stability, and purified NH₄Cl/CHOOK target products. In-situ spectroscopic studies and theoretical calculations reveal that both heterogeneous interfaces and oxygen vacancies optimize the electronic structure of R-Ag@Co₃O_4-x, significantly lowering the reaction energy barrier of the rate-determining step and accelerating the hydrogenation kinetics of N-containing intermediates for efficient NH₃ production.