Copper (II) Heterocyclic Thiosemicarbazone Complexes as Single-Source Precursors for the Preparation of Cu9S5 Nanoparticles: Application in Photocatalytic Degradation of Methylene Blue

Abstract

In this study, two copper(II) complexes, [Cu(C6H8N3S2)2]Cl2 (1) and [Cu(C7H10N3S2)2]Cl2·H2O (2), were synthesized from 2-(thiophen-2-ylmethylene)hydrazine-1-carbothioamide (L1H) and 2-(1-(thiophen-2-yl)ethylidene)hydrazine-1-carbothioamide (L2H) respectively and characterized using various spectroscopic techniques and elemental analyses. The as-prepared complexes were used as single-source precursors for the synthesis of oleylamine-capped (OLA@CuxSy), hexadecylamine-capped (HDA@CuxSy), and dodecylamine-capped (DDA@CuxSy) copper sulphide nanoparticles (NPs) via the thermolysis method at 190 °C and 230 °C and then characterized using powder X-ray diffraction (p-XRD), UV-visible spectroscopy, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The p-XRD diffraction patterns confirmed the formation of crystalline rhombohedral digenite Cu9S5 with the space group R-3m. The TEM images showed the formation of nanoparticles of various shapes including hexagonal, rectangular, cubic, truncated-triangular, and irregularly shaped Cu9S5 nanomaterials. The SEM results showed aggregates and clusters as well as the presence of pores on the surfaces of nanoparticles synthesized at 190 °C. The UV-visible spectroscopy revealed a general blue shift observed in the absorption band edge of the copper sulphide NPs, as compared to bulk CuxSy, with energy band gaps ranging from 2.52 to 3.00 eV. Energy-dispersive X-ray spectroscopy (EDX) confirmed the elemental composition of the Cu9S5 nanoparticles. The nanoparticles obtained at 190 °C and 230 °C were used as catalysts for the photocatalytic degradation of methylene blue (MB) under UV irradiation. Degradation rates varying from 47.1% to 80.0% were obtained after 90 min of exposure time using only 10 mg of the catalyst, indicating that Cu9S5 nanoparticles have potential in the degradation of organic pollutants (dyes).