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Investigation of Atomically Precise Nanostructures for Electrocatalytic Conversion of CO2

Nagarajan, Anantha Venkataraman (2023) Investigation of Atomically Precise Nanostructures for Electrocatalytic Conversion of CO2. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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In order to alleviate the high concentrations of CO2 while meeting increasing demands for chemicals and fuels, electrochemical CO2 reduction reaction (CO2RR) has gained tremendous interest. A vast array of nanomaterials have been investigated as electrocatalysts that can reliably convert CO2 to valuable fuels and chemicals. However, understanding the atomic level behavior of nanomaterials during CO2RR remains a complex challenge. Overcoming this challenge will result in the rapid, targeted development of nanomaterials that can significantly promote circular economy. Ligand-protected metal nanoclusters (LPNCs) are a remarkable class of nanomaterials (1-3 nm in diameter) with unique physicochemical properties that can outperform larger, conventional nanoparticles (NPs) for CO2RR. Importantly, their atomically precise structures provide a platform to unravel accurate mechanistic insight into CO2RR through accurate computational methods such as Density Functional Theory (DFT). This work elucidates the detailed behavior of LPNCs during CO2RR while also building a foundation for the rapid discovery of new, highly active LPNCs for electrocatalytic applications. First, we showcased the stability of a range of LPNCs during CO2RR through the Thermodynamic Stability Model (TSM). Importantly, we rationalized the experimentally observed stability of the well-known Au25 LPNC during CO2RR. Next, we expanded the nanomaterials domain of interest and elucidated the experimentally observed higher CO2RR performance of Au-based LPNCs modified via heterometal doping and ligand engineering. At the same time, we uncovered the nature of catalytically active sites on LPNCs during CO2RR. Lastly, we provided a descriptor-based framework for the accelerated screening of electrocatalytically active alloy LPNCs. Overall, this dissertation provides important insights into the electrocatalytic behavior of LPNCs and their applicability towards sustainable fuels and chemicals production.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Nagarajan, Anantha Venkataramanann76@pitt.eduann76
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairMpourmpakis, GiannisGMPOURMP@pitt.eduGMPOURMP
Committee MemberKeith, Johnjakeith@pitt.edujakeith
Committee MemberMcKone, Jamesjmckone@pitt.edujmckone
Committee MemberWang, Guofengguw8@pitt.eduguw8
Committee MemberKauffman,
Date: 19 January 2023
Date Type: Publication
Defense Date: 19 August 2022
Approval Date: 19 January 2023
Submission Date: 25 October 2022
Access Restriction: 1 year -- Restrict access to University of Pittsburgh for a period of 1 year.
Number of Pages: 99
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: electrochemistry, computational catalysis, atomic precision
Date Deposited: 19 Jan 2023 19:13
Last Modified: 19 Jan 2024 06:15


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