Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 33, Pages 11467-11469Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja1055615
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Funding
- Rutgers University
- NSF [DMR-0541911, 0966829]
- [AFOSR-FA9550-05-1-0365]
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [966829] Funding Source: National Science Foundation
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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, lambda-MnO2 center dot LiMn2O4 is not a catalyst for water oxidation. Upon removal of the lithium, the cubical Mn4O4 cores become active sites for oxidizing water to molecular oxygen, which was investigated with the photochemical [Ru2+(2,2'-bpy)(3)]/persulfate system at pH 5.8. The nanosize lambda-MnO2 obtained from the nanocrystalline LiMn2O4, which was synthesized by the citrate route, shows a significantly higher water oxidation catalytic activity (Turnover Frequency: 3 x 10(-5) MOl O-2/s/mol Mn) than that obtained via solid state reaction with micrometer and irregular particle sizes (Turnover Frequency: 5 x 10(-6) mol O-2/s/mol Mn).
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