Water Oxidation by λ-MnO2

Catalysis by the Cubical Mn4O4 Subcluster Obtained by Delithiation of Spinel LiMn2O4

David M. Robinson, Yong Bok Go, Martha Greenblatt, G Charles Dismukes

Research output: Contribution to journalArticle

199 Citations (Scopus)

Abstract

Nanocrystalline spinel LiMn2O4 has been prepared and treatment of LiMn2O4 with dilute nitric acid solution resulted in the delithiation of the framework, while maintaining the spinel structure, λ-MnO2. LiMn2O4 is not a catalyst for water oxidation. Upon removal of the lithium, the cubical Mn 4O4 cores become active sites for oxidizing water to molecular oxygen, which was investigated with the photochemical [Ru 2+(2,2′-bpy)3]/persulfate system at pH 5.8. The nanosize λ-MnO2 obtained from the nanocrystalline LiMn 2O4, which was synthesized by the citrate route, shows a significantly higher water oxidation catalytic activity (Turnover Frequency: 3 × 10-5 mol O2/s/mol Mn) than that obtained via solid state reaction with micrometer and irregular particle sizes (Turnover Frequency: 5 × 10-6 mol O2/s/mol Mn).

Original languageEnglish
Pages (from-to)11467-11469
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number33
DOIs
Publication statusPublished - Aug 25 2010

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Catalysis
Oxidation
Water
Nitric Acid
Molecular oxygen
Nitric acid
Solid state reactions
Lithium
Particle Size
Citric Acid
Catalyst activity
Catalytic Domain
Particle size
Oxygen
Catalysts
spinell
lithium manganese oxide

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Water Oxidation by λ-MnO2 : Catalysis by the Cubical Mn4O4 Subcluster Obtained by Delithiation of Spinel LiMn2O4. / Robinson, David M.; Go, Yong Bok; Greenblatt, Martha; Dismukes, G Charles.

In: Journal of the American Chemical Society, Vol. 132, No. 33, 25.08.2010, p. 11467-11469.

Research output: Contribution to journalArticle

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AB - Nanocrystalline spinel LiMn2O4 has been prepared and treatment of LiMn2O4 with dilute nitric acid solution resulted in the delithiation of the framework, while maintaining the spinel structure, λ-MnO2. LiMn2O4 is not a catalyst for water oxidation. Upon removal of the lithium, the cubical Mn 4O4 cores become active sites for oxidizing water to molecular oxygen, which was investigated with the photochemical [Ru 2+(2,2′-bpy)3]/persulfate system at pH 5.8. The nanosize λ-MnO2 obtained from the nanocrystalline LiMn 2O4, which was synthesized by the citrate route, shows a significantly higher water oxidation catalytic activity (Turnover Frequency: 3 × 10-5 mol O2/s/mol Mn) than that obtained via solid state reaction with micrometer and irregular particle sizes (Turnover Frequency: 5 × 10-6 mol O2/s/mol Mn).

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