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

ABSTRACT

Electrochemical nitrite reduction reaction ( NO 2 - 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 NO 2 - 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 ( r N H 3 ${{r}_{{\mathrm{N}}{{{\mathrm{H}}}_{\mathrm{3}}}}}$ ) of 946.1 µg h-1 m cat - 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.