Journal
INORGANIC CHEMISTRY
Volume 57, Issue 12, Pages 6873-6882Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b00461
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Funding
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences [KC040602, DE-AC05-00OR22725]
- Scientific User Facilities Division, Office of Basic Sciences, U.S. DOE
- U.S. DOE, Office of Science [DE-AC02-06CH11357, DE-SC0012704]
- Office of Vehicle Technologies of the U.S. DOE through the Advanced Battery Materials Research Program [DE-SC0012704]
- National Science Foundation [OIA 1355438, DMR 1455154]
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Layered delta-MnO2 (birnessites) are ubiquitous in nature and have also been reported to work as promising water oxidation catalysts or rechargeable alkali-ion battery cathodes when fabricated under appropriate conditions. Although tremendous effort has been spent on resolving the structure of natural/synthetic layered delta-MnO2 in the last few decades, no conclusive result has been reached. In this Article, we report an environmentally friendly route to synthesizing homogeneous Cu-rich layered delta-MnO2 nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered delta-MnO2 has been successfully resolved from combined Mn/Cu K-edge extended X-ray fine structure spectroscopy and X-ray and neutron total scattering analysis. It is found that appreciable amounts (similar to 8%) of Mn vacancies are present in the MnO2 layer and Cu2+ occupies the interlayer sites above/below the vacant Mn sites. Effective hydrogen bonding among the interlayer water molecules and adjacent layer O ions has also been observed for the first time. These hydrogen bonds are found to play the key role in maintaining the intermediate and long-range stacking coherence of MnO2 layers. Quantitative analysis of the turbostratic stacking disorder in this compound was achieved using a supercell approach coupled with anisotropic particle-size-effect modeling. The present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.
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