Low temperature scalable synthetic approach enabling high bifunctional electrocatalytic performance of NiCo2S4 and CuCo2S4 thiospinels

Ginena Bildard Shombe; Shumaila Razzaque; Malik Dilshad Khan; Tebello Nyokong; Philani Mashazi; Jonghyun Choi; Sanket Bhoyate; Ram K. Gupta; Neerish Revaprasadu

doi:10.1039/D1RA02309H

Low temperature scalable synthetic approach enabling high bifunctional electrocatalytic performance of NiCo₂S₄ and CuCo₂S₄ thiospinels†

Ginena Bildard Shombe,^ab Shumaila Razzaque,^c Malik Dilshad Khan,

*^ad Tebello Nyokong,

^e Philani Mashazi,

^ef Jonghyun Choi,^g Sanket Bhoyate,^g Ram K. Gupta^g and Neerish Revaprasadu

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of Zululand, Private Bag X1001, KwaDlangezwa 3880, South Africa
E-mail: RevaprasaduN@unizulu.ac.za, malikdilshad@hotmail.com

^b Chemistry Department, University of Dar es Salaam, P.O. Box 35061, Dar es Salaam, Tanzania

^c Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Luoyu Road No. 1037, Wuhan, China

^d Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

^e Institute for Nanotechnology Innovation, Rhodes University, P.O. Box 94, Makhanda 6140, South Africa

^f Department of Chemistry, Rhodes University, P. O. Box 94, Makhanda 6140, South Africa

^g Department of Chemistry, Pittsburg State University, Pittsburg, KS 66762, USA

Abstract

Ternary metal sulfides are currently in the spotlight as promising electroactive materials for high-performance energy storage and/or conversion technologies. Extensive research on metal sulfides has indicated that, amongst other factors, the electrochemical properties of the materials are strongly influenced by the synthetic protocol employed. Herein, we report the electrochemical performance of uncapped NiCo₂S₄ and CuCo₂S₄ ternary systems prepared via solventless thermolysis of the respective metal ethyl xanthate precursors at 200 and 300 °C. The structural, morphological and compositional properties of the synthesized nanoparticles were examined by powder X-ray diffraction (p-XRD), transmission electron microscopy (TEM), high-resolution TEM, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) techniques. Electrochemical studies indicate that NiCo₂S₄ nanoparticles synthesized at 300 °C exhibit superior energy storage characteristics with a high specific capacitance of ca. 2650 F g⁻¹ at 1 mV s⁻¹, as compared to CuCo₂S₄ nanoparticles, which showcased a specific capacitance of ca. 1700 F g⁻¹ at the same scan rate. At a current density of 0.5 A g⁻¹, NiCo₂S₄ and CuCo₂S₄ nanoparticles displayed specific capacitances of 1201 and 475 F g⁻¹, respectively. In contrast, CuCo₂S₄ nanoparticles presented a higher electrocatalytic activity with low overpotentials of 269 mV for oxygen evolution reaction (OER), and 224 mV for the hydrogen evolution reaction (HER), at 10 mA cm⁻². The stability of the catalysts was examined for 2000 cycles in which a negligible change in both OER and HER activities was observed.

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Low temperature scalable synthetic approach enabling high bifunctional electrocatalytic performance of NiCo₂S₄ and CuCo₂S₄ thiospinels†

Abstract

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Low temperature scalable synthetic approach enabling high bifunctional electrocatalytic performance of NiCo₂S₄ and CuCo₂S₄ thiospinels

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