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

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).

Testing the Efficacy of the Synthesis of Iron Antimony Sulfide Powders from Single Source Precursors

The antimony-iron sulfide system in general does not produce alloys below 540 °C from traditional solid-state methods. However, single source precursors have been known to produce unexpected products that arise from kinetically trapped polymorphs. In this paper, we test the efficacy of this approach toward the Fe-Sb-S system. Antimony and iron diethyldithiocarbamate complexes of the form Sb[S2CN(Et2)]3 (1) and Fe[S2CN(Et2)]3 (2) were synthesised, characterised, and used as single-source precursors for the preparation of Sb2S3, FexSy, and mixed iron antimony sulfide Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1) powders using the solvent-less thermolysis method at different temperatures ranging from 300 to 475 °C. The effect of different mole fractions of the iron precursor was evaluated on morphology, shape, and optical and magnetic properties of Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1). The obtained powders were characterized by X-ray diffraction (XRD), Raman spectroscopy scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, magnetometer measurement, and UV/vis/NIR spectroscopy. The results demonstrated that the crystalline structure, morphology, and elemental composition of the samples changed with the mole fraction of the precursor. There was significant phase separation between Sb and Fe sulfides noted from EDX spectroscopic mapping, yet an optoelectronic study monitoring the direct band gap energy of antimony sulfide shows that the band gap energy increases as a function of Fe content, which suggests limited alloying is possible from the single source route.

Di-tert-butyltin(IV) 2-pyridyl and 4,6-dimethyl-2-pyrimidyl thiolates: versatile single source precursors for the preparation of SnS nanoplatelets as anode material for lithium ion batteries

New air and moisture stable diorganotin complexes derived from 2-mercaptopyridine (HSpy) [tBu2Sn(Spy)2], [tBu2Sn(Cl)(Spy)] and 4,6-dimethyl-2-mercaptopyrimidine (HSpymMe2) [tBu2Sn(Cl)(SpymMe2)] have been prepared and utilized as single source molecular precursors for the preparation...

Catalytically active nanosized Pd9Te4 (telluropalladinite) and PdTe (kotulskite) alloys: first precursor-architecture controlled synthesis using palladium complexes of organotellurium compounds as single source precursors

First precursor-architecture controlled synthesis of Pd9Te4 and PdTe nanostructures that have potential applications in Suzuki coupling of 4-chlorobenzaldehyde and catalytic reduction of 4-nitrophenol.