TY - JOUR
T1 - Revealing and Rationalizing the Rich Polytypism of Todorokite MnO2
AU - Hu, Xiaobing
AU - Kitchaev, Daniil A.
AU - Wu, Lijun
AU - Zhang, Bingjie
AU - Meng, Qingping
AU - Poyraz, Altug S.
AU - Marschilok, Amy C.
AU - Takeuchi, Esther S.
AU - Takeuchi, Kenneth J.
AU - Ceder, Gerbrand
AU - Zhu, Yimei
N1 - Funding Information:
The electron microscopy work at BNL is supported by the U.S. Department of Energy, Office of Basic Energy Science, Division of Materials Science and Engineering, under Contract No. DESC0012704. The materials synthesis and bulk characterization, including TEM experiments conducted by X.H., were supported as part of the Center for Mesoscale Transport Properties, an Energy Frontier Research Center supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0012673. D.K. and G.C. acknowledge support for the computational analysis from the Center for Next-Generation of Materials by Design, an Energy Frontier Research Center funded by U.S. Department of Energy, Office of Basic Energy Science. The computational analysis was performed using computational resources provided by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562, as well as computational resources sponsored by the Department of Energy’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/6/6
Y1 - 2018/6/6
N2 - Polytypism, or stacking disorder, in crystals is an important structural aspect that can impact materials properties and hinder our understanding of the materials. One example of a polytypic system is todorokite-MnO2, which has a unique structure among the transition-metal oxides, with large ionic conductive channels formed by the metal oxide framework that can be utilized for potential functionalization, from molecular/ion sieving to charge storage. In contrast to the perceived 3 × 3 tunneled structure, we reveal a coexistence of a diverse array of tunnel sizes in well-crystallized, chemically homogeneous one-dimensional todorokite-MnO2. We explain the formation and persistence of this distribution of tunnel sizes thermochemically, demonstrating the stabilization of a range of coherent large-tunnel environments by the intercalation of partially solvated Mg2+ cations. Based on structural behavior of the system, compared to the common well-ordered alkali-stabilized polymorphs of MnO2, we suggest generalizable principles determining the selectivity of structure selection by dopant incorporation.
AB - Polytypism, or stacking disorder, in crystals is an important structural aspect that can impact materials properties and hinder our understanding of the materials. One example of a polytypic system is todorokite-MnO2, which has a unique structure among the transition-metal oxides, with large ionic conductive channels formed by the metal oxide framework that can be utilized for potential functionalization, from molecular/ion sieving to charge storage. In contrast to the perceived 3 × 3 tunneled structure, we reveal a coexistence of a diverse array of tunnel sizes in well-crystallized, chemically homogeneous one-dimensional todorokite-MnO2. We explain the formation and persistence of this distribution of tunnel sizes thermochemically, demonstrating the stabilization of a range of coherent large-tunnel environments by the intercalation of partially solvated Mg2+ cations. Based on structural behavior of the system, compared to the common well-ordered alkali-stabilized polymorphs of MnO2, we suggest generalizable principles determining the selectivity of structure selection by dopant incorporation.
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U2 - 10.1021/jacs.8b02971
DO - 10.1021/jacs.8b02971
M3 - Article
C2 - 29733635
AN - SCOPUS:85046757721
SN - 0002-7863
VL - 140
SP - 6961
EP - 6968
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 22
ER -