Pt‐Mediated Co‐Adsorption of Hydroxyl and Nitrogen‐Heterocyclic Species Over Cu/CuO Heterostructure Enhances Coupled Azotriazole Electrosynthesis and Dual‐Electrode Hydrogen Production

Abstract

ABSTRACT Electrocatalytic N─N oxidative coupling (OC) offers an eco‐friendly approach to produce value‐added azo materials, but suffers from sluggish kinetics and limited Faradaic efficiency (FE). The key fundamental issue is unfavorable competitive adsorption of hydroxyl groups and N ‐heterocyclic species. Here, a Pt‐immobilized Cu/CuO heterostructure is designed to create energy‐favorable N─N OC of N ‐heterocyclic diaminotriazole (DATOC). Operando spectroscopy along with theoretical calculations reveal that the immobilization of Pt nanoclusters (NCs) in Cu/CuO mediates adsorption capacities for both N ‐heterocyclic substrates/intermediates and OH − species on Cu sites of Cu/CuO, collaboratively promoting DATOC kinetics. While the N─N intermediates are effectively adsorbed on Pt─Cu sites via metal–N coordination. Consequently, the Pt@Cu/CuO catalyst only requires 0.832 and 0.904 V RHE to achieve 10 and 100 mA cm −2 , respectively, with a high FE of 95%. Due to the low‐potential DATOC, the adsorbed hydrogen atom from N─H cleavage of aminotriazole undergoes counterintuitive self‐coupling to H 2 . As a result, the dual‐electrode H 2 production requires an electricity input of only 1.15 kWh per m 3 of H 2 . The exceptional catalytic durability of the coupled system is also demonstrated in a flow electrolyzer for 600 h@500 mA cm −2 . This work provides a new perspective for highly efficient green azo electrosynthesis and low‐energy‐consumption H 2 production.