Date of Award

Summer 8-2016

Degree Type

Dissertation

Degree Name

Ph.D.

Degree Program

Chemistry

Department

Chemistry

Major Professor

John B. Wiley

Abstract

The ability to encapsulate/insert different kinds of nanoparticles (NPs) in scrolled nanosheets (NSs) may lead to the formation of new nanocomposite materials that yield novel properties. These nanostructures resemble “peapods” that consist of NPs chains (“peas”) located in a hollow space of desired nanoscrolls (“pods”). Depending on different combinations of “peas” and “pods” diverse families of nanopeapods (NPPs) can be synthesized which may exhibit interesting properties not accessible from the individual components. Though there exist various synthetic methods for the formation of NPPs, more development in terms of simplicity, flexibility, and productivity of synthetic approaches are needed so that different classes of NPPs with unique combinations/characteristics of “peas” and “pods” can be synthesized.

A simple solvothermal synthesis method for the encapsulation of spherical Fe3O4 NPs by the capture of preformed NPs in scrolled hexaniobate has previously been developed in our group. In the first part of this research, efforts were made to extend the “pod” materials to other inorganic NScs. Vanadate nanoscrolls (NScs) could rapidly (2h) be produced using a simple solvothermal treatment in the presence of V2O5 as vanadium source, and either dodecylamine (DDA) or octadecylamine (ODA) as the structure-directing agent. The synthesis parameters were successfully adjusted to obtain high yields vanadate NScs (~ 20 g of NScs per synthesis) with different average lengths as 383 nm, 816 nm to 3.3 µm. The effects of reaction time on the formation of NScs were also investigated.

Further efforts focused on the development of methods for making vanadate NPPs. Here, two novel approaches for the formation of these NPPs have been successfully developed. In the first, solvothermal methods utilizing preformed Ag NPs and vanadate NSs lead to the formation of Ag@vanadate NPPs where NPs could be encapsulated during the scrolling of NSs. High NP loadings were acquired with this approach. In the second method, an insertion strategy was developed where Ag NPs were drawn into the lumen of preformed vanadate NScs upon controlled solvent evaporation. This method was also quite effective, though much lower loadings of NPs were achieved with larger average NP-NP distances. Also noteworthy in the study of vanadate NScs and NPPs is the observation of an uncommon asymmetric scrolling behavior; this was realized for both vanadate NScs and solvothermally synthesized Ag@vanadate NPPs.

Novel solvothermal approaches for the effective construction of organic-MoOx hybrid structures and MoOx nanosheets (NSs) have also been developed. These NSs can be controlled so as to exist in different oxidation states as well as in different crystal structures. Layer spacing as a function of organic molecule lengths could also be controlled by changing the type of surfactants located between the NSs. Individual NSs or a few layers of stacked NSs, up to four micrometers in lateral size were successfully prepared upon sonication. The effect of time, temperature, as well as the type of structure-directing agents on the formation and crystal structure of MoOx intercalated compound/NSs were also explored.

Lastly, a modified solvothermal method previously used for the encapsulation of spherical Fe3O4 NPs inside hexaniobate NScs was applied for the construction of cubic-CeO2 NPPs. High yield encapsulations of preformed cubic ~5 nm ceria NPs within the lumen of hexaniobate NScs were readily accomplished. Size selective encapsulation and the formation mechanism of cubic-CeO2 NPPs were also studied. Pre-organization and attachment of ceria NPs to the surface/edges of hexaniobate crystals prior to the scrolling process were observed, which is in a good agreement with our previous studies on the formation mechanism of NPPs. Partially filled CeO2@hexaniobate NPPs were further used in the in-situ growth of gold NPs within the empty/hollow space of hexaniobate NScs. This led to the formation of high-quality Au-CeO2@hexaniobate NPPs. We believe that smart combinations of the methods for the formation of NPPs, encapsulation, in-situ growth and insertion, will allow one to acquire other classes of nanocomposite materials composed of different types, shapes, and arrangements of NPs in the hollow spaces of distinct NTs/NScs.

Rights

The University of New Orleans and its agents retain the non-exclusive license to archive and make accessible this dissertation or thesis in whole or in part in all forms of media, now or hereafter known. The author retains all other ownership rights to the copyright of the thesis or dissertation.

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