Solution-Phase Synthesis of Nanoparticles and Growth Study
Authors:   , Cheong Soshan 
Published: November 2021

<p>This thesis is concerned with solution-phase synthesis of nanoparticles and growth of nanoparticles in solution. A facile synthesis route was developed to produce nanoparticles of iron, iron carbide and ruthenium. In general, the synthesis involved the reaction/decomposition of a metal precursor in solution, in the presence of a stabilising agent, in a closed reaction vessel, under a hydrogen atmosphere. The crystallinity, crystal structure, morphology and chemical composition of the nanoparticles obtained were studied primarily by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (XRD), and energy dispersive X-ray spectroscopy (EDS). Scanning quantum interference device magnetometry (SQUID) was used to characterise the magnetic properties of iron and iron carbide nanoparticles. In situ synchrotron-based XRD was employed to investigate the growth of platinum nanoparticles of different morphologies.  The synthesis of iron and iron carbide nanoparticles was investigated at temperatures 80-160 °C. Syntheses at 130 °C and above produced mainly single-crystal α-Fe nanoparticles, whereas those at lower temperatures yielded products consisting of α-Fe and Fe₃C nanoparticles. Nanoparticles of larger than 10 nm oxidised on the surface leading to core/shell structures, and those of smaller size oxidised completely upon exposure to air. Core/shell nanoparticles of larger than 15 nm were observed to be stable under ambient conditions for at least a year, whereas those smaller in size underwent further oxidation forming core/void/shell structures. The magnetic properties of selected samples were characterised. The core/shell nanoparticles were shown to exhibit ferromagnetic behaviours, and saturation magnetisations were obtained at the range of 100-130 emu g⁻¹.  Nanoparticle size and size distribution, and morphology were found to be a result of combined effect of precursor concentration and the relative stabiliser concentration. In general, high-precursor concentration resulted in less controlled reaction and produced large nanoparticle size and size distribution. Under the high-concentration condition, the use of stabilisers in reduced amount then led to a diverse range of morphologies, which include dimer, porous and branched structures.  As for the synthesis of ruthenium nanoparticles, reactions of different precursors were investigated at temperatures ranging from room temperature to 140 °C. Highly crystalline ruthenium nanoparticles of different sizes and morphologies were obtained through different experimental conditions. The increase in nanoparticle size was found to be a result of increasing reaction temperature and/or decreasing stabiliser to ruthenium ratio. This trend was observed to be independent of the type of stabilisers and precursors used. The use of stabilisers with different binding characteristics has facilitated the formation of non-spherical nanoparticles; these include rod-like structures with high aspect ratios (of up to 12), hexagonal and truncated triangular plate-like structures, and tripods.  The growth of faceted and branched structures of platinum nanoparticles was investigated by employing in situ XRD techniques. TEM was used to examine the intermediate structures. The two different morphologies were previously shown to be governed by precursor concentration. It was found that the growth in the low-concentration reaction was characteristic of a thermodynamically controlled regime, whereas that in the high-concentration reaction occurred at much greater rates under a kinetically controlled regime. Based on the observations obtained, different growth mechanisms were proposed and discussed. The former involved an oriented attachment mechanism, while the latter, a novel mechanism involving selective growth and etching processes.  The results are followed by an overall discussion comparing and contrasting the various syntheses involved, and relating the results of syntheses to those of the growth studies.</p>