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Structure-property Relationships of Ligand-protected Metal Nanoclusters

Cowan, Michael James (2022) Structure-property Relationships of Ligand-protected Metal Nanoclusters. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Although nanomaterials find use in most technologies, a complete fundamental understanding of their property origins is missing. Solving this problem goes hand-in-hand with achieving structural determination of nanomaterials down to atomic-level precision, which would enable the use of theory to unravel important structure-property relationships (SPRs). Thiolate-protected metal nanoclusters (TPNCs) have attracted tremendous interest as a unique class of atomically precise nanomaterials. Since TPNC structures can be modulated through heterometal doping, the field offers an ideal space to systematically formulate new SPRs. Additionally, TPNCs exhibit physicochemical properties that are favorable for many applications, such as imaging cancer cells and catalysis. Thus, leveraging these "nano-models" for SPR development can directly impact many fields while simultaneously advancing our fundamental understanding of nanomaterials properties.
This work aims to develop, expand, and apply SPRs towards improved TPNC design for targeted applications. First, we demonstrated the application of the Thermodynamic Stability Model across all TPNC sizes. After introducing new IP and EA SPRs, we applied these models to a M21-M24 series of TPNCs, rationalizing the dopant-based stability observed under experiment. Next, we developed a simple framework that captures TPNC solubility behavior through molecular-like TPNC properties. We then used these properties to rationalize crystallization behavior in a series of TPNCs. Shifting focus to alloy systems, we extended our IP/EA SPRs to capture trends across AgAu TPNCs. Finally, we expanded the application of the Bond-Centric Model to capture stability of TPNCs. Remarkably, the new model rationalized the relative stability between experimentally determined TPNC isomers, revealing its promise as a tool to aid TPNC structure prediction. Overall, this dissertation provides new insights through SPRs that will fuel TPNC discovery towards property-and-application-targeted structure design.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Cowan, Michael Jamesmic132@pitt.edumic1320000-0001-8706-782X
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairMpourmpakis,
Committee MemberMillstone,
Committee MemberWilmer,
Committee MemberJin,
Date: 10 June 2022
Date Type: Publication
Defense Date: 15 December 2021
Approval Date: 10 June 2022
Submission Date: 29 December 2021
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 102
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: computational chemistry, metal nanoparticles, density functional theory, nanoparticle stability
Date Deposited: 10 Jun 2022 18:05
Last Modified: 10 Jun 2022 18:05

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