Efficient nitrite-glycerol paired electrolysis enabled by a MoO_x-modified Cu_0.81Ni_0.19 alloy electrode

Paired electrolysis integrating the nitrite reduction reaction (NO₂RR) with the glycerol oxidation reaction (GOR) offers an energy-efficient strategy for simultaneously producing value-added chemicals. Herein, we report a defect-rich amorphous MoO_x cluster-decorated Cu_0.81Ni_0.19 alloy electrode (CuNi(MoO_x)/NF) featuring a strongly coupled oxide/alloy interface as a highly efficient electrocatalyst for both NO₂RR and GOR. The optimal catalyst exhibits promising performance, delivering a maximum NH₃ Faradaic efficiency (FE) of 96.1% with an NH₃ production rate of 1.06 mmol h^-1 cm^-2 for NO₂RR, together with a formate FE of 96.1% and a production rate of 1.34 mg h^-1 cm^-2 for GOR. Operando spectroscopic characterizations combined with electrochemical analyses reveal that the interfacial MoO_x species effectively accelerate reaction kinetics of both NO₂RR and GOR. Consequently, the CuNi(MoO_x)/NF enables energy-efficient paired electrolysis in a membrane electrode assembly, requiring only 1.47 V to reach 200 mA cm^-2 while maintaining stable NH₃ and formate production for over 300 h. It also exhibits outstanding performance in a rechargeable Zn-NO₂^- battery with a peak power density of 10.14 mW cm^-2 and high cycling stability, highlighting its versatility for practical electrochemical energy conversion.