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Title: Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds

Abstract

Abstract The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M I dimeric complexes with M−M bonding, [M 2 (en) 2 ] 2+ , (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor‐type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en) 2 ] 2+ . Here, the facile interconversion between dimeric‐M I and monomeric‐M II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X‐ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M 2 (en) 2 ] 2+ or [M(en) 2 ] 2+ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M 0 →M 2+ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry Oregon State University Corvallis Oregon 97331-4003 United States
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1631493
Grant/Contract Number:  
DE SC0010802
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal Journal Volume: 26 Journal Issue: 36; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Xu, Wei, Kozma, Karoly, Sha, Tianxiang, Wu, Yi‐Jen, Nyman, May, and Lerner, Michael M. Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds. Germany: N. p., 2020. Web. doi:10.1002/chem.202000504.
Xu, Wei, Kozma, Karoly, Sha, Tianxiang, Wu, Yi‐Jen, Nyman, May, & Lerner, Michael M. Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds. Germany. https://doi.org/10.1002/chem.202000504
Xu, Wei, Kozma, Karoly, Sha, Tianxiang, Wu, Yi‐Jen, Nyman, May, and Lerner, Michael M. Tue . "Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds". Germany. https://doi.org/10.1002/chem.202000504.
@article{osti_1631493,
title = {Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds},
author = {Xu, Wei and Kozma, Karoly and Sha, Tianxiang and Wu, Yi‐Jen and Nyman, May and Lerner, Michael M.},
abstractNote = {Abstract The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M I dimeric complexes with M−M bonding, [M 2 (en) 2 ] 2+ , (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor‐type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en) 2 ] 2+ . Here, the facile interconversion between dimeric‐M I and monomeric‐M II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X‐ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M 2 (en) 2 ] 2+ or [M(en) 2 ] 2+ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M 0 →M 2+ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.},
doi = {10.1002/chem.202000504},
journal = {Chemistry - A European Journal},
number = 36,
volume = 26,
place = {Germany},
year = {Tue Jun 02 00:00:00 EDT 2020},
month = {Tue Jun 02 00:00:00 EDT 2020}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/chem.202000504

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Cited by: 2 works
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