Influence of Ligand Structure on Excited State Surface Chemistry of Lead Sulfide Quantum Dots

Kennehan, Eric R.; Munson, Kyle T.; Grieco, Christopher; Doucette, Grayson S.; Marshall, Ashley R.; Beard, Matthew C.; Asbury, John B.

doi:10.1021/jacs.1c06248

Influence of Ligand Structure on Excited State Surface Chemistry of Lead Sulfide Quantum Dots

Journal Article · Sat Aug 21 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c06248· OSTI ID:1819077

Kennehan, Eric R. ^[1]; Munson, Kyle T. ^[2]; Grieco, Christopher ^[1]; Doucette, Grayson S. ^[2]; Marshall, Ashley R. ^[3]; ^[3]; ^[2]

Magnitude Instruments, State College, PA (United States); Pennsylvania State Univ., University Park, PA (United States)
Pennsylvania State Univ., University Park, PA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)

The ligand-nanocrystal boundaries of colloidal quantum dots (QDs) mediate the primary energy and electron transfer processes that underpin photochemical and photocatalytic transformations at their surfaces. We use mid-infrared transient absorption spectroscopy to reveal the influence that ligand structure and bonding to nanocrystal surfaces have on the changes of the excited state surface chemistry of this boundary in PbS QDs and the corresponding impact on charge transfer processes between nanocrystals. We demonstrate that oleate ligands undergo marked changes in their bonding to surfaces in the excitonic excited states of the nanocrystals, indicating that oleate passivated PbS surfaces undergo significant structural changes following photoexcitation. These changes can impact the surface mobility of the ligands and the ability of redox shuttles to approach the nanocrystal surfaces to undergo charge transfer in photocatalytic reactions. In contrast, markedly different transient vibrational features are observed in iodide/mercaptoproprionic acid passivated PbS QD films that result from charge transfer between neighboring nanocrystals and localization of holes at the nanocrystal surfaces near MPA ligands. This ability to distinguish the influence that excitonic excited states vs charge transfer processes have on the surface chemistry of the ligand-nanocrystal boundary lays the groundwork for exploration of how this boundary can be understood and controlled for the design of nanocrystalline materials tailored for specific applications in solar energy harvesting and photocatalytic reactions.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308; SC0019349

OSTI ID:: 1819077

Alternate ID(s):: OSTI ID: 1839363

Report Number(s):: NREL/JA--5900-80322; MainId:42525; UUID:ea01d019-4575-49f7-bb3f-9426993a9d43; MainAdminID:61708

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 34 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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