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Synthesis of nickel sulfide and nickel–iron sulfide nanoparticles from nickel dithiocarbamate complexes and their photocatalytic activities
Authors:Subbiah Thirumaran  Govindasamy Gurumoorthy  Rajaram Arulmozhi  Samuele Ciattini
Institution:1. Department of Chemistry, Annamalai University, Annamalai Nagar, 608 002 India;2. Department of Chemistry, Annamalai University, Annamalai Nagar, 608 002 India

Department of Chemistry, Bharath Institute of Higher Education and Research (BIHER), Bharath University, Chennai, Tamil Nadu, 600073 India;3. Department of Chemistry, SRM IST, Kattankulathur, Tamil Nadu, 603 203 India;4. Centro di Cristallografia Strutturale, Polo Scientifico di Sesto Fiorentino, Via della Lastruccia No.3,50019, Sesto Fiorentino, Firenze, Italy

Abstract: Ni(dtc)2] (dtc = N-(pyrrole-2-ylmethyl)-N-thiophenemethyldithiocarbamate ( 1 ), N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamate ( 2 ), N-furfuryl-N-methylferrocenyldithiocarbamate ( 3 ), and (N-pyrrole-2-ylmethyl]-N-thiophenemethyldithiocarbamato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II) ( 4 ) complexes were prepared and characterized by elemental analysis, infrared, ultraviolet–visible, and nuclear magnetic resonance (1H and 13C) spectroscopies. The data were consistent with the formation of square planar nickel(II) complexes, which was confirmed by single-crystal X-ray diffraction studies on 2 and 4 . Fe···Fe interactions exhibited by complex 2 led to supramolecular aggregation. The structure of 4 reveals intermolecular and intramolecular C-H···Ni anagostic interactions. The anion-sensing properties of 2 were studied with halide ions by cyclic voltammetry. It was observed that 2 acts as sensor for bromide. Complexes 1 , 2 , and 3 , were utilized to prepare nickel sulfide, nickel–iron sulfide-1, and nickel–iron sulfide-2, respectively. The composition, structure, morphology, and optical properties of nickel sulfide and nickel–iron sulfides were examined using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, ultraviolet–visible, fluorescence, and infrared spectroscopy. Powder X-ray diffraction patterns of nickel sulfide, nickel–iron sulfide-1, and nickel–iron sulfide-2 indicate the formation of orthorhombic Ni9S8, cubic NiFeS2, and cubic Ni2FeS4, respectively. The photocatalytic activities of as-prepared nickel sulfide and nickel–iron sulfide-1 nanoparticles were investigated for photodegradation of methylene blue and rhodamine-B under ultraviolet irradiation. Nickel–iron sulfide-1 nanoparticles show slightly higher photodegradation efficiency compared with the nickel sulfide nanoparticles.
Keywords:dye degradation  nickel(II)dithiocarbamates  nickel–iron sulfide  nickel sulfide  single-source precursors
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