Elsevier

Materials Letters

Volume 64, Issue 2, 31 January 2010, Pages 136-139
Materials Letters

Characterization of copper sulfide nanostructured spheres and nanotubes synthesized by microwave-assisted solvothermal method

https://doi.org/10.1016/j.matlet.2009.10.021Get rights and content

Abstract

Copper sulfide nanostructured spheres and nanotubes were successfully synthesized, using a microwave-assisted solvothermal method, by the decomposition of [Cu(CH3CSNH2)2]Cl2 complexes, formed by the reaction of CuCl2·2H2O and CH3CSNH2 in ethylene glycol at different pH values, and identified by CHNS/O and FTIR analyses. The decrease in bonding energy of N–H revealed the coordination of copper ions and thioacetamide molecules. It was specified that nitrogen atoms of thioacetamide molecules were used to form Cu–thioacetamide complexes. XRD, SEM, TEM and SAED analyses show that the products were hexagonal CuS spheres in an extremely low pH solution, and hexagonal CuS nanotubes at a pH 13. Their Raman spectra show sharp peaks at 473 cm 1, identified as the S–S stretching mode of S2 ions at the 4e sites.

Introduction

Copper sulfides are materials with different chemical formulae, ranging from copper rich (Cu2S) to sulfur rich (CuS2). They are widely used for different applications, such as p-type semiconductors, thermoelectric and photoelectric converters, high capacity cathode materials in lithium secondary batteries, solar radiation absorbers and nonlinear optical materials [1], [2], [3], [4], depending on their stoichiometries and complex structures—including valence states of copper and sulfur atoms. Different shapes and sizes of the sulfides, such as nanocones [1], hollow spheres [3], nanoplates [4], nanobelts [1], [5] and nanostructured flowers [6], were synthesized through various methods—including a facile precipitate-converting reaction [3], hydrothermal/solvothermal routes [1], [4], [6], and chemical method in combination with solvothermal route [5].

The microwave-assisted solvothermal synthesis has more advantage than the conventional solvothermal one, due to the rapid heating to a temperature of heat treatment, by increasing the kinetics of reaction by one to two orders of magnitude, leading to the formation of some novel phase with high crystallinity in the chemical system. This explanation shows the microwave-assisted solvothermal synthesis that is very rapid as compared to the conventional solvothermal reaction [7], [8], [9]. It is therefore for us to present the development of copper sulfide nanostructured spheres and nanotubes using the microwave-assisted solvothermal method.

Section snippets

Experiment

The 5 mmol each of CuCl2·2H2O and CH3CSNH2 was dissolved in 40 ml ethylene glycol with different pH values, adjusted by KOH solution. The reactions proceeded in an acid digestion bomb (Parr Instrument Company) using 50% of 180 W microwave irradiation for 20 min. At the end of the process, the precipitates were washed with water and ethanol, and dried at 80 °C for 12 h.

The products were analyzed using an elemental analyzer (2400 Series II CHNS/O Analyzer Perkin Elmer) with cystine as a calibrating

Results and discussion

Thioacetamide is an organic sulfur compound with the formula of CH3CSNH2. It has lone pair electrons on nitrogen and sulfur atoms, and is able to donate lone pair electrons to form coordination compound with the vacant d-orbital of Cu cations. By adding thioacetamide and copper chloride in ethylene glycol solutions, light-green precipitates (Cu–thioacetamide complexes) were synthesized. The complexes were analyzed using CHNS/O analyzer and Fourier transform infrared (FTIR) spectroscopy. CHNS/O

Conclusions

By using a microwave-assisted solvothermal method, hexagonal CuS was successfully synthesized by the decomposition of [Cu(CH3CSNH2)2]Cl2 complexes. FTIR and CHNS/O analyses showed the formation, thermal stability and atomic ratio of [Cu(CH3CSNH2)2]Cl2 complexes. XRD patterns showed hexagonal CuS structure, corresponding to the SAED pattern. The Raman wavenumber was detected at 473 cm 1, assigned to be the S–S stretching mode of S2 ions at the 4e sites. Their morphologies were characterized using

Acknowledgement

The research was supported under the National Research University Project for Chiang Mai University, by the Commission on Higher Education, Ministry of Education, Thailand.

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