Paired electrolysis employing both anodic and cathodic half reactions for the synthesis of value-added chemicals is an ultimate energy-efficient approach. Here, we show that paired reductive coupling of nitroaromatics into azoxy-aromatics and oxidative coupling of aromatic amines into azo-aromatics can be realized with high efficiency and selectivity employing the surfacehydroxylated Ni 3 Fe metal−organic framework (Ni 3 Fe-MOF-OH) bifunctional electrocatalyst. The competitive hydrogen and oxygen evolution reactions are suppressed due to the adsorption of nitroarenes and anilines via surface hydroxyls of the electrocatalyst. Simultaneous cathodic and anodic N−N coupling of a wide range of nitroaromatics and aniline derivatives are realized with high conversion and selectivity at an overall bias of 1.4 V in an undivided cell in 1 M KOH electrolyte. Ni 3 Fe-MOF-OH displays a high stability and enables gram-scale synthesis of azo-and azoxy-aromatics with a satisfactory yield and Faraday efficiency, offering an efficient synthetic protocol for applications.

Durable Cu/NiFe(OH)x electrocatalyst are designed for hydrogen evolution reaction in alkaline media. The in-situ generated Cu nanodendrites protect the NiFe(OH)x from being hydrogenated, endorsing it a >1000 h lifetime for...