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On the active sites and mechanisms of cobalt and manganese water oxidation catalysts

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Title
On the active sites and mechanisms of cobalt and manganese water oxidation catalysts
Name (type = personal)
NamePart (type = family)
Smith
NamePart (type = given)
Paul F.
NamePart (type = date)
1988-
DisplayForm
Paul F. Smith
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Dismukes
NamePart (type = given)
Charles
DisplayForm
Charles Dismukes
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
chair
Name (type = corporate)
NamePart
Rutgers University
Role
RoleTerm (authority = RULIB)
degree grantor
Name (type = corporate)
NamePart
Graduate School - New Brunswick
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (encoding = w3cdtf); (qualifier = exact)
2015
DateOther (qualifier = exact); (type = degree)
2015-10
CopyrightDate (encoding = w3cdtf); (qualifier = exact)
2015
Place
PlaceTerm (type = code)
xx
Language
LanguageTerm (authority = ISO639-2b); (type = code)
eng
Abstract (type = abstract)
The “holy grail” of renewable, sustainable energy is artificial replication of the only natural process capable of storing sun energy into chemical bonds: Photosynthesis. The oxidation of water to molecular O2 is the thermodynamic bottleneck to this process. As such, viable catalysts for water oxidation are warranted. These materials ideally 1) are constructed of abundant elements (e.g., first row transition metals) and thus affordable, 2) operate efficiently and effectively with little applied bias (overpotential), and 3) maintain high activity for useful lifetimes. In Chapter 1, Nature’s CaMn4O5 “heterocubane” catalyst is introduced. Principles of this structure which must translate into artificial catalysts are discussed: O-O bond formation, sacrificing oxidizing strength for long lifetimes, and effective storage of oxidizing equivalents via proton-coupled electron transfer (expanded in Chapter 5). In Chapters 2-3, this thesis addresses the reactivity of cobalt based catalysts. Crystalline and amorphous cobalt oxides are well-known oxygen evolving catalysts, but up to three different mechanisms are proposed to occur on their surfaces. While the “cubane” topology is stressed as biomimetic, these mechanisms commonly only feature a single metal active site- seemingly negating the cubane topology as necessary for catalysis. The results in these chapters- via studies on discrete Co2O2, Co3O3 and Co4O4 clusters- demonstrate that the cubane topology optimally stabilizes the Co4+ oxidation state via delocalization across all metal centers. This stored oxidizing equivalent reacts with terminally bound OH- sites and facilitates oxidation fully to O2. In Chapter 4, this thesis addresses the reactivity of manganese-based catalysts. Paradoxical observations are known: Nature’s effectiveness at utilizing Mn have predominantly translated into poor artificial Mn catalysts. While partially explained by the ~30 possible structures of Mn-oxides (many of which are minerals), promising results have correlated activity with stabilization of Mn3+, as opposed to Mn4+. The studies shown here rationalize these paradoxes by comparing structural polytypes of Mn3+, clearly demonstrating that corner-sharing, labile Mn3+ centers capable of facile water binding correlate with catalytic activity as found in both layered and tunnel Mn oxides. Conversely, Mn of any oxidation state in strongly coupled structures are effective at storing charge but not transferring it to water.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
Subject (authority = ETD-LCSH)
Topic
Catalysts
Subject (authority = ETD-LCSH)
Topic
Cobalt
Subject (authority = ETD-LCSH)
Topic
Manganese catalysts
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_6847
PhysicalDescription
Form (authority = gmd)
electronic resource
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application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xvi, 214 p. : ill.)
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Paul F. Smith
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier (type = doi)
doi:10.7282/T39P33NP
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The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Smith
GivenName
Paul
MiddleName
F.
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2015-09-30 20:50:02
AssociatedEntity
Name
Paul Smith
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - New Brunswick
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License
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Author Agreement License
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
RightsEvent
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2015-10-31
DateTime (encoding = w3cdtf); (qualifier = exact); (point = end)
2016-10-30
Type
Embargo
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after October 30th, 2016.
Copyright
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Copyright protected
Availability
Status
Open
Reason
Permission or license
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