Activity enhancement of Ru/CeO2 for N-alkylation of amines with alcohols through tailoring metal-support interaction
Activity enhancement of Ru/CeO2 for N-alkylation of amines with alcohols through tailoring metal-support interaction
复制标题
DOI：
10.1016/j.jcat.2023.115241
复制
发表时间：
2023-12
影响因子：
7.3
通讯作者：
Yiwen Zou;Lin Dong;Siyang Yan;Jiaxu Liu;Lili Mu;Licheng Li;Yue Hu;Haifeng Qi;Shanjun Mao;Zupeng Chen
中科院分区：
文献类型：
--
作者：
Yiwen Zou;Lin Dong;Siyang Yan;Jiaxu Liu;Lili Mu;Licheng Li;Yue Hu;Haifeng Qi;Shanjun Mao;Zupeng Chen
胺与醇的高效、选择性N-烷基化反应是一个重要而又极具挑战性的研究课题。本文报道了以苯甲醇和苯胺为原料，在不同的Ru/CeO 2催化剂上合成N-苄基苯胺（BZA）的反应。其中Ru/CeO 2-R（棒状）催化剂的活性最高，BZA的转化率高达88%，明显高于Ru/CeO 2-C（立方体，52%）和Ru/CeO 2-O（八面体，32%）催化剂。大量的实验研究表明，金属态的Ru纳米颗粒促进了羟基的脱氢和亚胺的加氢，而富氧空位的CeO 2-R有利于反应物的吸附和活化。动力学研究和时间分辨双光束傅里叶变换红外光谱分析证实了苯甲醇的转移加氢反应历程，即苯甲醇首先脱氢生成苯甲醛，然后与苯胺自发反应，最后快速转化为N-苄基苯胺。
Efficient and selectiveN-alkylation of amines with alcoholsviatransfer hydrogenation is of great significance but extremely challenging. Here, we report the production ofN–benzylaniline (BZA) from benzyl alcohol and aniline over various fine-shaped Ru/CeO2catalysts. The Ru/CeO2–R (rod) catalyst exhibits the highest catalytic activity among all catalysts, in which the yield of BZA reaches up to 88% with complete conversion, significantly higher than that of Ru/CeO2-C (cube, 52%) and Ru/CeO2-O (octahedron, 32%). Extensive experimental investigations disclose that Ru nanoparticles with a metallic state promote the dehydrogenation of the hydroxyl group and hydrogenation of imines, while the CeO2–R with rich oxygen vacancies facilitates the adsorption and activation of reactants. Furthermore, kinetic studies and time-resolvedoperandodual-beam Fourier transform infrared spectroscopy analysis confirms the transfer hydrogenation pathway, in which the benzyl alcohol is firstly dehydrogenated to benzaldehyde, followed by spontaneously reacting with aniline, and finally transforms into theN-benzylaniline rapidly.