Zeolite-encapsulated copper(ii) complexes with NNO-tridentate Schiff base ligands: catalytic activity for methylene blue (MB) degradation under near neutral conditions

Abstract

Three novel copper Schiff base complexes, L¹Cu(OAc)–L³Cu(OAc), bearing NNO tridentate ligands were synthesized and successfully entrapped in zeolite. All free and encapsulated complexes were fully characterized through experiments combined with theoretical calculations, and were subsequently employed as catalysts to activate H₂O₂ for degradation of methylene blue (MB). The catalytic activity of free complexes was tunable by substitution effects. The complex L³Cu(OAc) displayed enhanced efficiency by adopting bulky and donor substitutions due to the lower oxidation states. However, the free complexes exhibited modified structural and catalytic properties upon encapsulation into the zeolite. The constraint from the zeolite holes and coordination geometry caused the alteration of electronic structures and subsequently modified the reactivity. This study revealed that upon encapsulation, the larger molecular dimension of L³Cu(OAc) resulted in additional distorted geometry, leading to higher catalytic efficiency for MB degradation with more blue shifts in the UV-Vis spectrum. There was high catalytic activity by LⁿCu(OAc)-Y compared to that of the free complex, and high recyclability under near neutral conditions. In addition, the catalytic efficiency of L³Cu(OAc)-Y was higher or equivalent compared to other catalysts. This work provides new complexes with NNO tridentate ligands encapsulated inside zeolite and explains the relationship between the modified structure and functionality.