Quaternary medium-entropy nanoalloys with crystalline/amorphous heterointerfaces for highly selective and stable photocatalytic nitrite reduction to ammonia

Abstract Photocatalytic reduction of nitrite (NO2−) to ammonia (NH3) presents a sustainable path for wastewater remediation and nitrogen resource recovery. However, the sluggish seven-proton/six-electron (7H+/6e−) transfer kinetics and the formidable energy barrier of hydrogen atom transfer (HAT) limit its practical efficiency. Herein, we report a robust photocatalyst comprising quaternary medium entropy alloy (MEA) nanoparticles (Cu, Co, Ni, Zn) anchored on TiO2 nanosheets (TNS), featuring a tailor-made crystalline/amorphous heterointerfaces. The unique interfacial architecture synergistically optimizes the bidentate adsorption of nitrite and accelerates water dissociation, thereby lowering the activation energy for active hydrogen (*H) generation. Benefiting from the high-entropy-induced “sluggish diffusion” effect, the amorphous domains exhibit exceptional structure stability against photo-induced recrystallization. Consequently, the HH-CCNZ@TNS catalyst achieves a remarkable NH3 production efficiency of 99.69% with near 100% selectivity, maintaining superior durability over multiple cycles. This work underscores the potential of entropy engineering in coordinating multi-step proton/electron dynamics for advanced energy and environmental catalysis.