Mohammadi Leila, Hosseinifard Mojtaba, Vaezi Mohammad Reza, Rostamnia Sadegh
Department of Nano Technology and Advanced Materials, Materials and Energy Research Center Karaj Iran
Department of Energy, Materials and Energy Research Center Karaj Iran
RSC Adv. 2023 Feb 7;13(7):4843-4858. doi: 10.1039/d2ra07700k. eCollection 2023 Jan 31.
In this research a highly efficient and heterogeneous catalyst of ZSM-5@APTMS@()-4-((pyridin-2-ylimino)methyl) benzaldehyde@Cu-NPs was synthesized for upgrading the A coupling reaction for the synthesis of propargylamines under mild conditions. Rational tuning of the microenvironment of metallic NPs to improve efficiency and reusability in catalytic performances is of significance for scalable applications. Firstly, ZSM-5 was immobilized with APTMS (3-aminopropyltrimethoxysilane) and further modified with ()-4-((pyridin-2-ylimino)methyl)benzaldehyde. Subsequently, the amine-activated zeolite@()-4-((pyridin-2-ylimino)methyl)benzaldehyde was applied to increase the stabilization of Cu metal nanoparticles. The catalyst was treated with hydrazine to reduce Cu(ii) to Cu(0), which led to active metal sites. The results of catalytic performance in comparison with different parts of catalysis indicate high efficiency due to the stabilization of copper nanoparticles onto the newly synthesized support of MOF modified with nitrogen aromatic groups. The addition of N-rich organic ligand through modification alters the electronic structure of the final composite in favor of the progress of the A-coupling reaction. Moreover, the proposed catalyst showed no reduction in the catalytic performance up to four cycles, and a minor loss of efficiency occurs after the seventh cycle. In addition, the catalyst was effectively recycled up to 7 times without leaching of Cu-NPs.
在本研究中,合成了一种高效的多相催化剂ZSM-5@APTMS@()-4-((吡啶-2-基亚氨基)甲基)苯甲醛@Cu-NPs,用于在温和条件下促进用于合成炔丙胺的A耦合反应。合理调节金属纳米颗粒的微环境以提高催化性能的效率和可重复使用性对于可扩展应用具有重要意义。首先,用APTMS(3-氨丙基三甲氧基硅烷)固定ZSM-5,并进一步用()-4-((吡啶-2-基亚氨基)甲基)苯甲醛进行改性。随后,将胺活化的沸石@()-4-((吡啶-2-基亚氨基)甲基)苯甲醛用于提高铜金属纳米颗粒的稳定性。用肼处理该催化剂,将Cu(ii)还原为Cu(0),从而产生活性金属位点。与催化不同部分相比的催化性能结果表明,由于铜纳米颗粒在新合成的含氮芳基修饰的MOF载体上的稳定化,催化效率很高。通过改性添加富氮有机配体改变了最终复合材料的电子结构,有利于A耦合反应的进行。此外,所提出的催化剂在四个循环内催化性能没有降低,在第七个循环后效率略有损失。此外,该催化剂可有效循环使用7次,且没有Cu-NPs的浸出。