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- Materials such as ternary MIMIIIE2 (where MI = Ag, Cu; MIII = In, Fe; E = S, Se) chalcopyrite-type nanocrystals have garnered interest recently because of their size- and composition-tunable electronic and optical properties. However, controlling the composition of multinary compounds is challenging due to the difference in reactivity of the involved components. Metal–organic precursors usually provide better control over stoichiometry due to preformed bonds. Herein, we have synthesized suitable sulfur-based (dihexyldithiocarbamato) and selenium-based (tetradiphenylimidodiselnodiphosphanate) metal-organic precursors of iron for the preparation of phase pure ternary CuFeS2 and CuFeSe2 nanocrystals, via hot injection route using oleylamine as solvent, decomposition initiator and capping agent. The nanomaterials were characterized by powder-X-ray diffraction (p-XRD), high resolution-transmission electron microscopy (HR-TEM), TEM, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and ultraviolet–visible (UV–Vis) analysis. The effect of temperature on synthesized nanoparticles was also investigated, showing that the size and morphology change from particles to sheet-like structures. The band gap of synthesized nanomaterials also showed variation along with the temperature change. The study shows a facile route for composition and morphologically controlled ternary chalcopyrite nanomaterials.
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- Different alkyl xanthate complexes of cobalt (alkyl = Ethyl, Hexyl, Octyl) were synthesized and used for the synthesis of nanoparticles by a solvent-less route. The p-XRD of the nanoparticles showed the formation of the CoS phase only from all precursors. The effect of size and surface capping on energy generation and energy storage applications was investigated. The electrocatalytic performance of the synthesized samples for hydrogen (HER) and oxygen evolution reaction (OER), indicates that CoS synthesized from the octyl xanthate complex (CoS-Oct) showed higher electrocatalytic performance. A lower over potential of 325 mV and 200 mV was observed for CoS-Oct, at a current density of 10 mA/cm2, for OER and HER, respectively. The charge storage performance was also investigated, where an inverse trend was observed i.e. the highest specific capacitance (1500 F/g, at scan rate 2 mV/s) was observed for the CoS sample synthesized from ethyl xanthate (CoS-ET). Similarly, the discharge time for CoS-ET was longer as compared to the other samples, suggesting better performance for the charge storage applications. The use of cobalt xanthate complexes for the preparation of CoS by melt method, and the effect of self-capped and uncapped surface of CoS on supercapacitance and OER/HER performance, has never been investigated before.
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