Synthesis and Characterization of Aluminum Nanocrystals
| dc.contributor.advisor | Halas, Naomi J | |
| dc.creator | Jacobson, Christian Robert | |
| dc.date.accessioned | 2023-09-01T20:20:07Z | |
| dc.date.created | 2023-08 | |
| dc.date.issued | 2023-07-17 | |
| dc.date.submitted | August 2023 | |
| dc.date.updated | 2023-09-01T20:20:07Z | |
| dc.description | EMBARGO NOTE: This item is embargoed until 2025-08-01 | |
| dc.description.abstract | Aluminum nanocrystals (Al NCs) have emerged as a very promising optical material in recent years. Aluminum’s earth-abundance, localized surface plasmon resonance tunable from the IR to the deep UV, and relative stability due to a self-limiting oxide layer make it an appealing material for many applications. However, the extreme reactivity of many precursors required to produce Al NCs has limited research in this area. As a result, the synthesis, optical properties, and physical properties of Al NCs are not as well understood as metals such as gold and silver. While great strides have been made in controlled Al NC synthesis, a deeper understanding is required to allow for more complex and higher quality syntheses. Additionally, a more thorough understanding of their physical and optical properties will allow for better use of these particles and identification of potential applications. In this thesis, I present research delving into the optical properties, synthetic control, and oxidative stability of colloidal aluminum nanocrystals. In chapter 1, I will give a brief introduction to nanoparticle plasmonics, lay out the development of Al NC synthesis so far, and give a detailed description of Al NC synthesis. In chapter 2, I will present single-particle optical studies of two Al NC morphologies developed in the Halas lab, the first demonstrated anisotropic colloidal Al NCs and {100} faceted Al NCs (nanocubes). In chapter 3, I will present a novel Al NC synthesis utilizing the combination of titanium isopropoxide and Tebbe’s reagent to produce {100} Al NCs as small as 30 nm, currently the smallest synthesized Al NCs with clear shape control. Combining catalysts together is a strategy for Al NC synthesis that opens up a new avenue of synthesis design. In chapter 4, I will present a detailed study of the method by which titanocene catalysts control the shape of Al NCs. We demonstrate that titanocene catalysts bind to the particle surface and the particle morphology can be tuned from {100} to {111} by varying catalyst concentration. In chapter 5, I will present an investigation of the kinetics of alane reduction in Al NC synthesis indicating that the synthesis proceeds through a non-classical pathway. We show the existence of a metastable state decoupling the alane reduction from the particle growth, the understanding of which is crucial for rational design of new Al NC syntheses. In chapter 6, I will present studies of the impact of Al NC size, shape, and synthesis conditions on Al NC oxidation rates and mechanisms. Clear size-dependence, anomalous oxidation of nanowire clusters compared to spheres, and previously unknown changes to the nanocrystal oxide based on reaction conditions are examined. We demonstrate that the increased homogeneity of these particles compared to existing literature both requires and enables new research to understand the relationship between their morphology and their reactivity. This thesis expands understanding of the synthesis of Al NCs and their optical and physical properties, paving the way for future intelligent synthesis design and use of these particles in novel applications. | |
| dc.embargo.lift | 2025-08-01 | |
| dc.embargo.terms | 2025-08-01 | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.citation | Jacobson, Christian Robert. "Synthesis and Characterization of Aluminum Nanocrystals." (2023) Diss., Rice University. https://hdl.handle.net/1911/115256. | |
| dc.identifier.uri | https://hdl.handle.net/1911/115256 | |
| dc.language.iso | eng | |
| dc.rights | Copyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder. | |
| dc.subject | Plasmonics | |
| dc.subject | aluminum nanocrystals | |
| dc.subject | aluminum nanoparticles | |
| dc.subject | titanium isopropoxide | |
| dc.subject | titanocene | |
| dc.title | Synthesis and Characterization of Aluminum Nanocrystals | |
| dc.type | Thesis | |
| dc.type.material | Text | |
| thesis.degree.department | Chemistry | |
| thesis.degree.discipline | Natural Sciences | |
| thesis.degree.grantor | Rice University | |
| thesis.degree.level | Doctoral | |
| thesis.degree.name | Doctor of Philosophy |