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

doi:10.1021/ja1055615

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

Rutgers University

Research output: Contribution to journal › Article › peer-review

211 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 language	English
Pages (from-to)	11467-11469
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	132
Issue number	33
DOIs	https://doi.org/10.1021/ja1055615
Publication status	Published - Aug 25 2010

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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@article{d2c8945552f24e078eb4c633f1eb2258,

title = "Water Oxidation by λ-MnO2: Catalysis by the Cubical Mn4O4 Subcluster Obtained by Delithiation of Spinel LiMn2O4",

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).",

author = "Robinson, {David M.} and Go, {Yong Bok} and Martha Greenblatt and Dismukes, {G. Charles}",

year = "2010",

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TY - JOUR

T1 - Water Oxidation by λ-MnO2

T2 - Catalysis by the Cubical Mn4O4 Subcluster Obtained by Delithiation of Spinel LiMn2O4

AU - Robinson, David M.

AU - Go, Yong Bok

AU - Greenblatt, Martha

AU - Dismukes, G. Charles

PY - 2010/8/25

Y1 - 2010/8/25

N2 - 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).

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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