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From Metal Thiobenzoates to Metal Sulfide Nanocrystals: An Experimental and Theoretical Investigation
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
* Author to whom correspondence should be addressed.
Received: 15 March 2012; Accepted: 20 March 2012 / Published: 3 April 2012
Abstract: A simple preparation of metal sulfide nanoparticles via the decomposition of thiobenzoate precursors at room temperature is presented and discussed. Long chain alkylamines were found to mediate the breakdown of metal thiobenzoates, such as those containing Ag, Cu, In and Cd, to produce uniform Ag2S, Cu2−xS, In2S3 and CdS nanoparticles respectively. The long chain amines are assumed to play dual roles as the nucleophilic reagent and the capping agent. It was found that sizes of the nanoparticles can be controlled by changing the type of amine used, as well as the molar ratio between amine and the precursor. We performed DFT calculations on a proposed mechanism involving an initial nucleophilic addition of amine molecule onto the thiocarboxylates. The proposed reaction was also confirmed through the analysis of by-products via infrared spectroscopy. On the basis of this understanding, we propose to manipulate the stability of the precursors by coordination with suitable stabilizing groups, such that the reaction kinetics can be modified to generate different nanostructures of interest.
Keywords: metal sulfide nanoparticles; thiobenzoates; silver sulfide; copper sulfide; indium sulfide; cadmium sulfide
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Zhang, Z.; Lim, W.P.; Wong, C.T.; Xu, H.; Yin, F.; Chin, W.S. From Metal Thiobenzoates to Metal Sulfide Nanocrystals: An Experimental and Theoretical Investigation. Nanomaterials 2012, 2, 113-133.
Zhang Z, Lim WP, Wong CT, Xu H, Yin F, Chin WS. From Metal Thiobenzoates to Metal Sulfide Nanocrystals: An Experimental and Theoretical Investigation. Nanomaterials. 2012; 2(2):113-133.
Zhang, Zhihua; Lim, Wen Pei; Wong, Chiong Teck; Xu, Hairuo; Yin, Fenfang; Chin, Wee Shong. 2012. "From Metal Thiobenzoates to Metal Sulfide Nanocrystals: An Experimental and Theoretical Investigation." Nanomaterials 2, no. 2: 113-133.