Stabilization of copper nanoparticles onto the double Schiff-base-functionalized ZSM-5 for A3 coupling reaction catalysis aimed under mild conditions

Abstract

In this research a highly efficient and heterogeneous catalyst of ZSM-5@APTMS@(E)-4-((pyridin-2-ylimino)methyl) benzaldehyde@Cu-NPs was synthesized for upgrading the A³ 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 (E)-4-((pyridin-2-ylimino)methyl)benzaldehyde. Subsequently, the amine-activated zeolite@(E)-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 A³-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.