Guanshu Zhao, Chengliang Mao, Shuai Yue, Shufang Ji, Lucy Wu, Andrew Wang, Kaiwen Zheng, Chengqi Tao, G. A. Ozin
ABSTRACT Sunlight‐driven catalytic urea synthesis offers a sustainable ambient‐pressure pathway for fertilizer production, but energy‐intensive liquid‐urea separation limits its practicality. Non‐aqueous photothermal urea synthesis from gaseous NH 3 and CO 2 offers a promising alternative, though molecular activations under dry and mild conditions remain challenging. Here, we report photothermal urea synthesis over Ru nanocrystals supported on acidic Al 2 O 3 , basic MgO, and neutral SiO 2 , achieving an optimal rate of 2745.71 ± 46.91 µmol urea g Ru −1 h −1 , an order‐of‐magnitude higher than state‐of‐the‐arts at ambient pressure. Mechanistic studies elucidate a reaction pathway, initiated photothermally by Ru and orchestrated by an acidic chemical environment that promoted the availability of reactants, in which exothermic N–H bond dissociation of NH 3 matches endothermic C–N coupling with CO 2 in a thermodynamically favorable manner. This work demonstrates an ultra‐efficient pioneering synthesis paradigm under near‐ambient conditions, circumventing industrial reliance on harsh thermochemical conditions.