Redirecting surface reconstruction of CoP-Cu heterojunction to promote ammonia synthesis at industrial-level current density

Directional reconstructed CoP-Cu/Co(OH) 2 promotes the synergistic catalysis of NO 3 − RR to deliver satisfactory ammonia production rate (9.91 mmol h −1 cm −2 ) and high Faraday efficiency (99.2 %) with appreciable economic benefits at industrial-level current densities . • Self-supported CoP-Cu heterojunction is successfully prepared by a simple method. • The reconstructed CoP-Cu/Co(OH) 2 boosted the NO 3 − RR performance via synergistic catalysis. • CoP-Cu/Co(OH) 2 delivers the NH 3 yield rate of 9.91 mmol h −1 cm −2 with the FE of 99.2 % at industrial-level current density. • The assembled MEA system can be operated efficiently and stably under industrial conditions. • Techno-economic analysis exhibits appreciable economic benefits of our system. The electrochemical reduction of nitrate (NO 3 − RR) represents a compelling approach for the treatment of wastewater, serving as both a sustainable substitute to the energy-intensive Haber-Bosch process and a viable alternative to direct electroreduction of N 2 . However, the process involves multiple electron and proton transfer steps and a complex reaction pathway, leading to low Faraday efficiency and selectivity. Herein, we demonstrated a directional surface reconstruction to generate CoP-Cu/Co(OH) 2 heterojunction for synergistic catalysis of NO 3 − RR. Impressively, a high ammonia generation rate of 9.91 mmol h −1 cm −2 and a Faraday efficiency of 99.2 % can be achieved at an industrial-relevant current density of 2 A cm −2 . Moreover, the catalyst exhibited exceptional durability, maintaining the activity for 110 h under industrial current density. Such outstanding NO 3 − RR performance can be ascribed to the synergistic catalytic effect among the active sites of Cu, CoP and Co(OH) 2 , as well as the excellent stability of self-supported catalyst. Specifically, Cu and CoP sites synergistically promote the conversion of NO 3 − to NO 2 − and NO 2 − to NH 3 . Meanwhile, the partial reconstructed Co(OH) 2 from CoP enhances water dissociation, thereby supplying active hydrogen (*H) essential for NO 3 − RR. When applied to a membrane electrode assembly (MEA) system, CoP-Cu/Co(OH) 2 can deliver satisfactory ammonia production rate with appreciable economic benefits at industrial-level current densities, highlighting its potential for industrial applications.