Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2

Liu, Jue; Yu, Lei; Hu, Enyuan; Guiton, Beth S.; Yang, Xiao -Qing; Page, Katharine

doi:10.1021/acs.inorgchem.8b00461

Title: Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO ₂

Journal Article · 30 May 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00461 · OSTI ID:1440358

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Kentucky, Lexington, KY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Layered δ-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 δ-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 δ-MnO₂ nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered δ-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 (~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. Furthermore, the present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1440358

Report Number(s):: BNL--205726-2018-JAAM

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite Shan, Xiaoqiang; Guo, Fenghua; Charles, Daniel S. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12939-3	journal	October 2019
Morphological evolution process of δ-MnO ₂ from 2-D to 1-D without phase transition Fu, Xin; Huo, Wangchen; Liu, Xiaoying CrystEngComm, Vol. 21, Issue 31 https://doi.org/10.1039/c9ce00715f	journal	January 2019
Hierarchical porosity via layer-tunnel conversion of macroporous δ-MnO ₂ nanosheet assemblies Metz, Peter C.; Ladonis, Alec C.; Gao, Peng RSC Advances, Vol. 10, Issue 3 https://doi.org/10.1039/c9ra08432k	journal	January 2020

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25 ENERGY STORAGE
birnessite
interlayer water
neutron diffraction
pair distribution function
stacking disorder
δ-MnO2

Title: Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2

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Title: Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO ₂