The Colloidal Chemistry Synthesis and Electron Microscopy Characterization of Shape-controlled Metal and Semiconductor Nanocrystals

Open Access
Author:
Biacchi, Adam Joseph
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
July 24, 2014
Committee Members:
  • Raymond Edward Schaak, Dissertation Advisor
  • Raymond Edward Schaak, Committee Chair
  • Thomas E Mallouk, Committee Member
  • Lasse Jensen, Committee Member
  • Robert Martin Rioux Jr., Committee Member
Keywords:
  • colloidal nanocrystals
  • shape-controlled nanoparticles
  • rhodium
  • tin sulfide
  • solution synthesis
  • HRTEM
Abstract:
Solution methods of materials synthesis have found application in a variety of fields due to the diversity of products accessible, facility of process scalability, and the ease of tuning their properties through prudent selection of reaction conditions. Control of experimental variables during the formation of colloidally stable nanoscale solids within a liquid matrix allows for tailoring of the particles’ characteristics, including shape, size, composition, and surface chemistry. In this dissertation, I will discuss how the manipulation of reaction chemistries can be used to synthesize shape-controlled metal and semiconductor colloidal nanocrystals. Further, I will elaborate on the mechanisms by which these particles form from molecular precursors and describe how their properties can differ from their bulk analogues through extensive characterization, especially using transmission electron microscopy. These studies contribute to the continued development of chemical routes to nanocrystals and their application as functional materials. First, I will review recent advances in the synthesis and characterization of shape-controlled nanocrystals, as well as highlight their promising applicability in a number of emerging technologies. These principles will then be leveraged to the specific case of catalytically-active rhodium nanocrystals, which can be synthesized with morphological and dimensional control using a polyol solution-mediated strategy. I describe an innovative shape-controlled synthesis to monodisperse colloidal rhodium icosahedra, cubes, triangular plates, and octahedra using this route. Additionally, new insights into the important role of the polyol reducing solvent on the synthesis of these nanocrystals are revealed, and how these might be exploited to engender superior reaction control and novel products. Next, I will describe how a crystallization mechanism was established for the synthesis of numerous morphologies of noble metal nanocrystals. I present a thorough analysis of the synthesis of shape-controlled rhodium nanocrystals, using extensive transmission electron microscopy characterization, and relate these findings to one of the primary synthetic levers available in the polyol synthesis: the anionic ligands present. Further, I show that the crystallization process proceeds by a nonclassical mechanism in which cluster particles serve as a stable intermediate between molecular precursors and the final product. I then apply these principles to the shape-controlled synthesis of other noble metal nanocrystals before expounding a generalized formation mechanism in the polyol synthesis of colloidal metal nanocrystals. Finally, I will highlight my efforts in the designed synthesis and characterization of colloidal tin(II) sulfide (SnS) semiconducting “quantum dot” nanocrystals. I describe a route for the solution synthesis of monodisperse colloidal SnS nanosheets, nanocubes, and nanospherical polyhedra in high yield. Further, detailed crystallographic characterization of these nanocrystals using transmission electron microscopy indicates that their atomic structure possesses a previously-unreported nanoscale deviation from the bulk phase. Additionally, I show that their electronic and photocatalytic properties of these quantum dots are both shape-dependent and distinct from bulk SnS.