Distinctive p‐d Orbital Hybridization in CuSb Porous Nanonetworks for Enhanced Nitrite Electroreduction to Ammonia

Electrochemical nitrite reduction reaction (NO2−RR${\mathrm{NO}}_{\mathrm{2}}^{\mathrm{ - }}{\mathrm{RR}}$), as a green and sustainable ammonia synthesis technology, has broad application prospects and environmental friendliness. Herein, an unconventional p‐d orbital hybridization strategy is reported to realize the fabrication of defect‐rich CuSb porous nanonetwork (CuSb PNs) electrocatalyst for NO2−RR${\mathrm{NO}}_{\mathrm{2}}^ - {\mathrm{RR}}$. The crystalline/amorphous heterophase structure is cleverly introduced into the porous nanonetworks, and this defect‐rich structure exposes more atoms and activated boundaries. CuSb PNs exhibit a large NH3 yield (rNH3${{r}_{{\mathrm{N}}{{{\mathrm{H}}}_{\mathrm{3}}}$) of 946.1 µg h−1 mcat−1${\mathrm{m}}_{{\mathrm{cat}}}^{ - {\mathrm{1}}}$ and a high faradaic efficiency (FE) of 90.7%. Experimental and theoretical studies indicate that the excellent performance of CuSb PNs results from the defect‐rich porous nanonetworks structure and the p‐d hybridization of Cu and Sb elements. This work describes a powerful pathway for the fabrication of p‐d orbital hybrid defect‐rich porous nanonetworks catalysts, and provides hope for solving the problem of nitrogen oxide pollution in the field of environment and energy. A defection‐rich CuSb porous nanonetworks (CuSb PNs) electrocatalyst is prepared for the conversion of nitrite to ammonia. The crystal/amorphous heterophase structure is cleverly introduced into the porous nanonetworks, and the unique p‐d orbital hybridization effect is used to regulate the activity. This work provides a powerful way to solve the nitrogen oxide pollution in the environmental and energy fields.