Concurrent Ammonia Synthesis and Alcohol Oxidation Boosted by Glutathione‐Capped Quantum Dots under Visible Light

Abstract

Mother nature accomplishes efficient ammonia synthesis via cascade N₂ oxidation by lightning strikes followed with enzyme‐catalyzed nitrogen oxyanion (NO_x⁻, x = 2,3) reduction. The protein environment of enzymatic centers for NO_x⁻‐to‐NH₄⁺ process greatly inspires the design of glutathione‐capped (GSH) quantum dots (QDs) for ammonia synthesis under visible light (440 nm) in tandem with plasma‐enabled N₂ oxidation. Mechanistic studies reveal that GSH induces positive shift of surface charge to strengthen the interaction between NO_x⁻ and QDs. Upon visible light irradiation of QDs, the balanced and rapid hole and electron transfer furnish GS⸱ radicals for 2e⁻/2H⁺ alcohol oxidation and H⸱ for 8e⁻/10H⁺ NO₃⁻‐to‐NH₄⁺ reduction simultaneously. For the first time, mmol‐scale ammonia synthesis is realized with apparent quantum yields of 5.45± 0.64%, and gram‐scale synthesis of value‐added acetophenone and NH₄Cl proceeds with 1:4 stoichiometry and stability, demonstrating promising multielectron and multiproton ammonia synthesis efficiency and sustainability with nature‐inspired artificial photocatalysts.

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