Qiqi Lu,Xiu-Zhi Wei,Haiyong Wang,Qi zhang,Xinghua Zhang,Lungang Chen,Jianguo Liu,Longlong Ma
The selective hydrogenation of nitrile represents an atom-economical and reliable method to synthesize primary amine, a privileged compound in chemistry, biology, and medicine. However, this approach often displays severe selectivity issues, and additives or reducing agents are generally required to solve this problem. In this work, we aim to synthesize primary amine on a green catalytic system and probe into the catalytic mechanism of Pd-Ni interaction using benzonitrile (BN) as a model compound. The nitrile hydrogenation reaction was catalyzed by bimetallic Pd-Ni oxide nanospecies confined in Silicalite‑1 (S-1) zeolite using H 2 as hydrogen donor without any additive which was environmentally friendly and economic. A 92% yield of benzylamine (BA) was achieved on the [email protected] catalyst with a turnover number (TON) of 1667, and such BA yield was still maintained in upscaling experiment. Detailed characterizations shed light on the mechanism of the extraordinary performance of Pd-Ni oxide nanospecies on base-free nitrile hydrogenation.
Selective hydrogenation of nitriles is a feasible route to synthesize primary amines. While highly desirable, conducting the synthesis under mild conditions is challenging. We report non-precious zinc and aluminum oxides supported Ni catalysts (Ni/ZnAlO x ) facilely prepared by calcination and reduction of NiZnAl layered double hydroxide (LDH) precursors. The optimized Ni/ZnAlO x -600 catalyst demonstrates great activity towards the selective hydrogenation of nitriles to primary amines. Proper-size metallic nickel provides the hydrogenation centers, and the presence of Ni-Zn alloys indicates strong metal-support interactions, which can produce electron-deficient nickel species and enhances the chemisorption of the C N bonds on the catalyst surface. The introduction of Zinc provides strong Lewis acid sites which also contribute to the catalytic activity. Based on the catalyst characterizations and control experiments, a plausible mechanism is proposed. This catalyst shows good stability and is conducive to the transformation of a variety of aromatic and aliphatic substrates, demonstrating potential application prospects.
危险品化学品经营许可证（带存储）