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Coordination Geometry and Oxidation State Requirements of Corner Sharing MnO6 Octahedra for Water Oxidation Catalysis: An Investigation of Manganite (γ-MnOOH)

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TitleInfo
Title
Coordination Geometry and Oxidation State Requirements of Corner Sharing MnO6 Octahedra for Water Oxidation Catalysis: An Investigation of Manganite (γ-MnOOH)
Name (type = personal)
NamePart (type = family)
Smith
NamePart (type = given)
Paul F.
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Deibert
NamePart (type = given)
Benjamin J.
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Kaushik
NamePart (type = given)
Shivam
Affiliation
Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Gardner
NamePart (type = given)
Graeme
Affiliation
Plant Biology and Pathology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Hwang
NamePart (type = given)
Shinjae
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Wang
NamePart (type = given)
Hao
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Al-Sharab
NamePart (type = given)
Jafar F.
Affiliation
Northwestern State University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Garfunkel
NamePart (type = given)
Eric
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Fabris
NamePart (type = given)
Laura
Affiliation
Materials Science and Engineering, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Li
NamePart (type = given)
Jing
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Dismukes
NamePart (type = given)
G. Charles
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (authority = RutgersOrg-Department); (type = corporate)
NamePart
Chemistry & Chemical Biology
Name (authority = RutgersOrg-School); (type = corporate)
NamePart
School of Arts and Sciences (SAS) (New Brunswick)
Name (authority = RutgersOrg-Department); (type = corporate)
NamePart
Plant Biology and Pathology
Name (authority = RutgersOrg-School); (type = corporate)
NamePart
School of Environmental and Biological Sciences (SEBS)
Name (authority = RutgersOrg-Department); (type = corporate)
NamePart
Materials Science and Engineering
Name (authority = RutgersOrg-School); (type = corporate)
NamePart
School of Engineering
Genre (authority = RULIB-FS)
Article, Refereed
Genre (authority = NISO JAV)
Accepted Manuscript (AM)
OriginInfo
DateIssued (encoding = w3cdtf); (keyDate = yes); (qualifier = exact)
2016
PhysicalDescription
InternetMediaType
application/pdf
Extent
11 p.
Extension
DescriptiveEvent
Type
Citation
AssociatedObject
Name
ACS Catalysis
Type
Journal
Relationship
Has part
Reference (type = url)
http://dx.doi.org/10.1021/acscatal.6b00099
Identifier (type = volume and issue)
6(3)
Detail
2089-2099
DateTime (encoding = w3cdtf)
2016
Language
LanguageTerm (authority = ISO 639-3:2007); (type = text)
English
Abstract (type = abstract)
Surface-directed corner-sharing MnO¬6 octahedra within numerous manganese oxide compounds containing Mn3+ or Mn4+ oxidation states show strikingly different catalytic activities for water oxidation, paradoxically poorest for Mn4+ oxides, regardless of oxidation assay (photochemical and electrochemical). This is demonstrated herein by comparing crystalline oxides consisting of Mn3+ (manganite, γ-MnOOH and bixbyite, Mn2O3), Mn4+ (pyrolusite, β-MnO2) and multiple monophasic mixed-valence manganese oxides. Like all Mn4+ oxides, pure β-MnO2 has no detectable catalytic activity, while γ-MnOOH (tetragonally distorted Mn3+O6, D4h symmetry) is significantly more active, and Mn2O3 (trigonal antiprismatic Mn3+O6, D3d symmetry) is the most active. γ-MnOOH deactivates during catalytic turnover simultaneous with the disappearance of crystallographically defined corner-sharing Mn3+O6 and the appearance of Mn4+. Comparing 2D-layered crystalline birnessites (δ-MnO2), the monovalent Mn4+ form is catalytically inert, while the hexagonal polymorph, containing few out-of-layer corner-sharing Mn3+O6, has ~10-fold higher catalytic activity than the triclinic polymorph, containing in-plane edge-sharing Mn3+O6. These electronic and structural correlations point towards the more flexible (corner shared) Mn3+O6 sites, over more rigid (edge shared) sites as substantially more active catalytic centers. Electrochemical measurements show and ligand field theory predicts that among corner shared Mn3+O6 sites, those possessing D3d ligand field symmetry have stronger covalent Mn-O bonding to the six equivalent oxygen ligands, which we ascribe as responsible for more efficient and faster electrolytic water oxidation. By contrast, D4h Mn3+O6 sites have weaker Mn-O bonding to the two axial oxygen ligands, separated electrochemical oxidation waves for Mn and O, and are catalytically less efficient and exhibit slower catalytic turnover. By controlling the ligand field geometry and strength to oxygen ligands we have identified the key variables for tuning water oxidation activity by manganese oxides. We apply these findings to propose a mechanism for water oxidation by the CaMn4O5 catalytic site of natural photosynthesis.
Subject (authority = LCSH)
Topic
Manganite
Subject (authority = LCSH)
Topic
Oxidation
Subject (authority = local)
Topic
Catalytic activity
Note (type = version identification)
This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acscatal.6b00099.
Note (type = peerReview)
Peer reviewed
RelatedItem (type = host)
TitleInfo
Title
Smith, Paul F.
Identifier (type = local)
rucore30179200001
RelatedItem (type = host)
TitleInfo
Title
Deibert, Benjamin J.
Identifier (type = local)
rucore30195300001
RelatedItem (type = host)
TitleInfo
Title
Gardner, Graeme
Identifier (type = local)
rucore30182800001
RelatedItem (type = host)
TitleInfo
Title
Hwang, Shinjae
Identifier (type = local)
rucore30195400001
RelatedItem (type = host)
TitleInfo
Title
Wang, Hao
Identifier (type = local)
rucore30179700001
RelatedItem (type = host)
TitleInfo
Title
Garfunkel, Eric
Identifier (type = local)
rucore30134900001
RelatedItem (type = host)
TitleInfo
Title
Fabris, Laura
Identifier (type = local)
rucore30195200001
RelatedItem (type = host)
TitleInfo
Title
Li, Jing
Identifier (type = local)
rucore30195500001
RelatedItem (type = host)
TitleInfo
Title
Dismukes, G. Charles
Identifier (type = local)
rucore30183300001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier (type = doi)
doi:10.7282/T3G44SBB
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RightsEvent
Type
Embargo
DateTime (encoding = w3cdtf); (point = start)
2016-02-10
DateTime (encoding = w3cdtf); (point = end)
2017-03-31
Detail
Access to this PDF has been restricted at the publisher's request. The publisher, ACS Publications, requires a 12 month embargo from the date the article was published. The article in this repository will be publicly available after March 31, 2017.
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Type
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Detail
This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acscatal.6b00099.
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American Chemical Society
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