水合物
联氨(抗抑郁剂)
化学计量学
催化作用
无机化学
晶体结构
化学
材料科学
物理化学
有机化学
色谱法
作者
Jinping Zhao,Ganping Wang,Yan Gao,Tongrui Wan,Jiaheng Qin,Xiao Zhang,Fangkun Sun,Jian Fang,Jiantai Ma,Yu Long
出处
期刊:ACS Sustainable Chemistry & Engineering
[American Chemical Society]
日期:2023-03-24
卷期号:11 (13): 5195-5205
被引量:12
标识
DOI:10.1021/acssuschemeng.2c07575
摘要
The metal-oxide-catalyzed transfer hydrogenation of nitroarenes to anilines by hydrazine hydrate has been widely reported; however, the risk of explosion resulting from excess hydrazine hydrate and high temperatures and complex preparations of these catalysts immensely hinder their industrial application. Herein, we use a simple co-precipitation method to synthesize atomically dispersed Ce-doped α-Fe2O3 (Ce0.025-Fe2O3-350 °C), which can completely reduce nitroarenes using stoichiometric hydrazine hydrate at room temperature, where the parent α-Fe2O3 is inactive. A thorough characterization indicates that the incorporation of Ce into the crystal lattice of α-Fe2O3 reorganizes the electronic structure of the surrounding Fe, such that the Lewis acidity of Fe2O3 is enhanced, which is the key for the room-temperature decomposition of N2H4·H2O. The structure is also beneficial for the adsorption of nitroarene, leading to the weakening of the N–O bonds. Mechanistic experiments and DFT calculations demonstrate that the reduction proceeds through Ph-NO2 → Ph-NHOH → Ph-NH2 without the widely recognized Ph-NO intermediate. Moreover, Ce0.025-Fe2O3-350 °C exhibits good stability in a continuous-flow reaction.
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