Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2
Abstract
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 tomore »
- Authors:
-
[1];
[3];
[2];
[3];
[1]
- 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)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1440358
- Report Number(s):
- BNL-205726-2018-JAAM
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 12; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; δ-MnO2; birnessite; interlayer water; pair distribution function; neutron diffraction; stacking disorder
Citation Formats
Liu, Jue, Yu, Lei, Hu, Enyuan, Guiton, Beth S., Yang, Xiao -Qing, and Page, Katharine. Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b00461.
Liu, Jue, Yu, Lei, Hu, Enyuan, Guiton, Beth S., Yang, Xiao -Qing, & Page, Katharine. Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2. United States. https://doi.org/10.1021/acs.inorgchem.8b00461
Liu, Jue, Yu, Lei, Hu, Enyuan, Guiton, Beth S., Yang, Xiao -Qing, and Page, Katharine. Wed .
"Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2". United States. https://doi.org/10.1021/acs.inorgchem.8b00461. https://www.osti.gov/servlets/purl/1440358.
@article{osti_1440358,
title = {Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2},
author = {Liu, Jue and Yu, Lei and Hu, Enyuan and Guiton, Beth S. and Yang, Xiao -Qing and Page, Katharine},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.8b00461},
journal = {Inorganic Chemistry},
number = 12,
volume = 57,
place = {United States},
year = {2018},
month = {5}
}
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Figures / Tables:
Figure 1: (a) SEM image, (b) TEM image and (c) XRD (synchrotron $λ$ = 0.414177 Å, $2θ$ converted to Cu K$α$ for clarity) pattern of the synthesized Cu-intercalated $δ$-MnO2. Miller indices are based on the reported monoclinic structure ($C$2/m) shown as an insert. The highlighted broad diffraction peaks (d ~more »
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Works referenced in this record:
Structure–Property Relationship of Bifunctional MnO 2 Nanostructures: Highly Efficient, Ultra-Stable Electrochemical Water Oxidation and Oxygen Reduction Reaction Catalysts Identified in Alkaline Media
journal, August 2014
- Meng, Yongtao; Song, Wenqiao; Huang, Hui
- Journal of the American Chemical Society, Vol. 136, Issue 32
The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries
journal, May 2015
- Nam, Kwan Woo; Kim, Sangryun; Lee, Soyeon
- Nano Letters, Vol. 15, Issue 6
The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese
journal, December 1971
- McKenzie, R. M.
- Mineralogical Magazine, Vol. 38, Issue 296
Nature of Activated Manganese Oxide for Oxygen Evolution
journal, November 2015
- Huynh, Michael; Shi, Chenyang; Billinge, Simon J. L.
- Journal of the American Chemical Society, Vol. 137, Issue 47
Mechanisms of pH-Dependent Activity for Water Oxidation to Molecular Oxygen by MnO 2 Electrocatalysts
journal, January 2012
- Takashima, Toshihiro; Hashimoto, Kazuhito; Nakamura, Ryuhei
- Journal of the American Chemical Society, Vol. 134, Issue 3
Crystal Structure Modeling of a Highly Disordered Potassium Birnessite
journal, January 1996
- Holland, Kerry L.
- Clays and Clay Minerals, Vol. 44, Issue 6
Determination of crystal structures with large known fragments directly from measured X-ray powder diffraction intensities
journal, June 1988
- Rius, J.; Miravitlles, C.
- Journal of Applied Crystallography, Vol. 21, Issue 3
Automatic structure determination from powder data with EXPO2004
journal, November 2004
- Altomare, Angela; Caliandro, Rocco; Camalli, Mercedes
- Journal of Applied Crystallography, Vol. 37, Issue 6
Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries
journal, August 2016
- Liu, Jue; Yin, Liang; Wu, Lijun
- Inorganic Chemistry, Vol. 55, Issue 17
Averaging the intensity of many-layered structures for accurate stacking-fault analysis using Rietveld refinement
journal, September 2016
- Coelho, Alan A.; Evans, John S. O.; Lewis, James W.
- Journal of Applied Crystallography, Vol. 49, Issue 5
3D Transition Metal Ordering and Rietveld Stacking Fault Quantification in the New Oxychalcogenides La 2 O 2 Cu 2–4 x Cd 2 x Se 2
journal, April 2016
- Ainsworth, Chris M.; Lewis, James W.; Wang, Chun-Hai
- Chemistry of Materials, Vol. 28, Issue 9
Rapid-acquisition pair distribution function (RA-PDF) analysis
journal, November 2003
- Chupas, Peter J.; Qiu, Xiangyun; Hanson, Jonathan C.
- Journal of Applied Crystallography, Vol. 36, Issue 6, p. 1342-1347
Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
- Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
- High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004
- Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
- Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012
- Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007
- Farrow, C. L.; Juhas, P.; Liu, J. W.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 33
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy
journal, May 2012
- Manceau, A.; Marcus, M. A.; Grangeon, S.
- American Mineralogist, Vol. 97, Issue 5-6
Relativistic Hartree–Fock X-ray and electron scattering factors
journal, May 1968
- Doyle, P. A.; Turner, P. S.
- Acta Crystallographica Section A, Vol. 24, Issue 3
Effective ionic radii in oxides and fluorides
journal, May 1969
- Shannon, R. D.; Prewitt, C. T.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 5
A fast and simple method for calculating electrostatic potentials
journal, August 1997
- Coelho, A. A.; Cheary, R. W.
- Computer Physics Communications, Vol. 104, Issue 1-3
Crystal structure of the sodium cobaltate deuterate superconductor
journal, December 2003
- Jorgensen, J. D.; Avdeev, M.; Hinks, D. G.
- Physical Review B, Vol. 68, Issue 21
Resolving the Structure of Ti 3 C 2 T x MXenes through Multilevel Structural Modeling of the Atomic Pair Distribution Function
journal, December 2015
- Wang, Hsiu-Wen; Naguib, Michael; Page, Katharine
- Chemistry of Materials, Vol. 28, Issue 1
Works referencing / citing this record:
Morphological evolution process of δ-MnO 2 from 2-D to 1-D without phase transition
journal, January 2019
- Fu, Xin; Huo, Wangchen; Liu, Xiaoying
- CrystEngComm, Vol. 21, Issue 31
Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite
journal, October 2019
- Shan, Xiaoqiang; Guo, Fenghua; Charles, Daniel S.
- Nature Communications, Vol. 10, Issue 1
Hierarchical porosity via layer-tunnel conversion of macroporous δ-MnO 2 nanosheet assemblies
journal, January 2020
- Metz, Peter C.; Ladonis, Alec C.; Gao, Peng
- RSC Advances, Vol. 10, Issue 3
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.