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dc.contributor.advisorWillets, Katherine A.
dc.creatorMonaghan, Joseph
dc.date.accessioned2023-05-22T20:11:38Z
dc.date.available2023-05-22T20:11:38Z
dc.date.issued2022
dc.identifier.urihttp://hdl.handle.net/20.500.12613/8587
dc.description.abstractIn this work, we use optical approaches to study and provide mechanistic insight into electrochemical reactions occurring at the surface of single nanoparticles. Correlated optical-electrochemical studies offer several advantages over single nanoparticle electrochemical studies including, higher spatial resolution, the ability to interrogate many nanoparticles at the same time and identify populations of inactive nanoparticles. Throughout this dissertation, two optical techniques are discussed in detail, dark-field scattering and super-localization imaging. In the first set of experiments, we describe calcite-assisted localization and kinetics (CLocK) microscopy, a multiparameter super-localization imaging technique. By placing a rotating birefringent calcite crystal in the infinity space of an optical microscope, CLocK provides immediate polarization and orientation information while still maintaining the ability to localize a single nanoparticle with < 10 nm resolution. Additionally, we demonstrate that the CLocK point spread function encodes kinetic information that we quantified to be an order of magnitude shorter than the integration time of the camera. In this work, CLocK provides new mechanistic insight into dynamic processes such as the dissolution of single gold nanorods as well as single-molecule surface-enhanced Raman scattering. In the second work, dark-field scattering was employed to monitor a proposed post-synthesis silver nanoparticle surface cleaning strategy to improve homogeneity across a population. Here, a sacrificial silver-sulfide sulfide shell is chemically grown on single silver nanoparticles to outcompete surface impurities. We demonstrate that upon electrochemical removal of the shell, a more reactive and reproducible silver surface can be achieved as revealed by enhanced electrodissoluion of the freshly cleaned silver nanoparticles. In these experiments, we additionally found a sulfide-dependent formation of multiple sulfide-species as well as mixed character sulfide shells on single nanoparticles themselves, thus demonstrating the sensitivity provided by optical microscopy at identifying multiple surface chemistries. Overall, the work in this dissertation highlights the ability of optical tools at revealing heterogeneity in single particle studies providing insight into structure-function relationships.
dc.language.isoeng
dc.publisherTemple University. Libraries
dc.relation.ispartofTheses and Dissertations
dc.rightsIN COPYRIGHT- This Rights Statement can be used for an Item that is in copyright. Using this statement implies that the organization making this Item available has determined that the Item is in copyright and either is the rights-holder, has obtained permission from the rights-holder(s) to make their Work(s) available, or makes the Item available under an exception or limitation to copyright (including Fair Use) that entitles it to make the Item available.
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subjectPhysical chemistry
dc.subjectAnalytical chemistry
dc.subjectNanoscience
dc.subjectElectrochemistry
dc.subjectNanoparticles
dc.subjectOptical microscopy
dc.subjectSilver nanoparticles
dc.subjectSilver sulfide
dc.subjectSingle entity
dc.titleOptical Approaches to Study Nanoscale Electrochemical Processes
dc.typeText
dc.type.genreThesis/Dissertation
dc.contributor.committeememberStrongin, Daniel R.
dc.contributor.committeememberSun, Yugang
dc.contributor.committeememberPatil, Chetan Appasaheb
dc.description.departmentPhysiology
dc.relation.doihttp://dx.doi.org/10.34944/dspace/8551
dc.ada.noteFor Americans with Disabilities Act (ADA) accommodation, including help with reading this content, please contact scholarshare@temple.edu
dc.description.degreePh.D.
dc.identifier.proqst15103
dc.creator.orcid0000-0002-5281-7130
dc.date.updated2023-05-18T19:07:01Z
refterms.dateFOA2023-05-22T20:11:39Z
dc.identifier.filenameMonaghan_temple_0225E_15103.pdf


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