Enzymatic Mesoporous Metal Nanocavities for Concurrent Electrocatalysis of Nitrate to Ammonia Coupled with Polyethylene Terephthalate Upcycling

Abstract Electrochemical upcycling of waste pollutants into high value‐added fuels and/or chemicals is recognized as a green and sustainable solution that can address the resource utilization on earth. Despite great efforts, their progress has seriously been hindered by the lack of high‐performance electrocatalysts. In this work, bimetallic PdCu mesoporous nanocavities (MCs) are reported as a new bifunctional enzymatic electrocatalyst that realizes concurrent electrocatalytic upcycling of nitrate wastewater and polyethylene terephthalate (PET) plastic waste. Abundant metal mesopores and open nanocavities of PdCu MCs provide the enzymatic confinement of key intermediates for the deeper electroreduction of nitrate and accelerate the transport of reactants/products within/out of electrocatalyst, thus affording high ammonia Faradic efficiency (FE NH3 ) of 96.6% and yield rate of 5.6 mg h −1 mg −1 at the cathode. Meanwhile, PdCu MC nanozymes trigger the selective electrooxidation of PET‐derived ethylene glycol (EG) into glycolic acid (GA) and formic acid with high FEs of >90% by a facile regulation of potentials at the anode. Moreover, concurrent electrosynthesis of value‐added NH 3 and GA is disclosed in the two‐electrode coupling system, further confirming the high efficiency of bifunctional PdCu MC nanozymes in producing value‐added fuels and chemicals from waste pollutants in a sustainable manner.