Revealing and Rationalizing the Rich Polytypism of Todorokite MnO2

Xiaobing Hu, Daniil A. Kitchaev, Lijun Wu, Bingjie Zhang, Qingping Meng, Altug S. Poyraz, Amy C. Marschilok, Esther S. Takeuchi, Kenneth J. Takeuchi, Gerbrand Ceder, Yimei Zhu*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)6961-6968
Number of pages8
JournalJournal of the American Chemical Society
Volume140
Issue number22
DOIs
StatePublished - Jun 6 2018

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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