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Ligand-Protected Nanocluster Stability, Doping, and Prediction

Taylor, Michael G. (2019) Ligand-Protected Nanocluster Stability, Doping, and Prediction. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Though new nanomaterials are synthesized every day for applications ranging from targeted drug delivery to chemical catalysis via ligand-stabilized colloidal growth methods, the physical underpinnings of these processes are often unknown. Without detailed knowledge of growth mechanisms or an understanding of the stability of the final product, synthesis of colloidal nanomaterials often relies on trial-and-error experimentation. Towards enabling nanomaterials-by-design, precise control of nanomaterial morphology (i.e. size, shape, chemical composition, and chemical ordering) is desired as morphology often dictates properties. To control morphology, an understanding of how nanomaterial structure relates to stability is needed. An ideal class of colloidal nanomaterials for studying structure-stability relations are atomically-precise the thiolate-protected metal nanoclusters (MNCs).

In this work, we focus on developing deeper understanding of the structure-related remarkable stability of MNCs and their physicochemical transformations utilizing ab-initio computational methods. First, we introduce a novel Thermodynamic Stability Model (TSM) for ligand-protected MNCs and demonstrate its power for understanding the stability of a wide range of MNCs. Next, we focus on the energetics of heterometal doping and ligand/dopant-mediated precise transformations of several smaller Au MNCs, showing remarkable agreement with experimental results. Finally, we demonstrate the application of the TSM to capture a wide range of experimental heterometal doping observations in Au25 MNCs for which no simple explanation previously existed. We also use the TSM to make predictions related to dopant locations and concentrations within the Au38 MNC.
Overall, this work advances knowledge of the underpinnings of the stability of ligand-protected atomically-precise MNCs contributing to MNC design for targeted applications.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Taylor, Michael G.mgt16@pitt.edumgt160000-0003-4327-2746
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairMpourmpakis, Giannisgmpourmp@pitt.edugmpourmp0000-0002-3063-0607
Committee MemberJohnson, Karl J.karlj@pitt.edukarlj0000-0002-3608-8003
Committee MemberWilmer, Christopherwilmer@pitt.eduwilmer0000-0002-7440-5727
Committee MemberJin, Rongchaorongchao@andrew.cmu.edu0000-0002-2525-8345
Date: 10 September 2019
Date Type: Publication
Defense Date: 2 May 2019
Approval Date: 10 September 2019
Submission Date: 24 April 2019
Access Restriction: 1 year -- Restrict access to University of Pittsburgh for a period of 1 year.
Number of Pages: 95
Institution: University of Pittsburgh
Schools and Programs: Swanson School of Engineering > Chemical and Petroleum Engineering
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Nanoclusters, Nanotechnology, Computational Chemistry
Date Deposited: 10 Sep 2019 18:10
Last Modified: 10 Sep 2020 05:15


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