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.
Highlights
The synthesis of metal sulfide nanocrystals has attracted much interest for both fundamental research and technological applications in the past decades [1,2,3,4,5,6]
Metal sulfide nanocrystals have been prepared by a wide range of synthetic methods, one of which involves the direct decomposition of molecular precursors [7,8,9,10,11,12,13,14]
We report a generalized precursor method operating at room temperature for the synthesis of various metal sulfide nanocrystals
Summary
The synthesis of metal sulfide nanocrystals has attracted much interest for both fundamental research and technological applications in the past decades [1,2,3,4,5,6]. Metal sulfide nanocrystals have been prepared by a wide range of synthetic methods, one of which involves the direct decomposition of molecular precursors [7,8,9,10,11,12,13,14]. One of the earliest precursors used for preparing metal sulfides in the literature is N,N’-dialkyl dithiocarbamate. In this preparation, the precursor was injected into hot coordination solvents such as trioctylphosphine oxide (TOPO) under nitrogen atmosphere at high temperatures [7,8,9,10,11]. It was found that Lewis base such as hexydecylamine (HDA), trioctylphosphine (TOP) or tributylphosphine (TBP)
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