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This content will become publicly available on May 7, 2019

Title: Revealing and Rationalizing the Rich Polytypism of Todorokite MnO 2

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–MnO 2, 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–MnO 2. 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 Mg 2+ cations. In conclusion, based on structural behavior of the system, compared to the common well-ordered alkali-stabilized polymorphs of MnO 2, we suggest generalizable principles determining the selectivity of structure selection by dopant incorporation.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [1] ;  [3] ;  [1] ;  [4] ; ORCiD logo [5] ; ORCiD logo [5] ; ORCiD logo [3] ;  [6] ; ORCiD logo [7]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Stony Brook Univ., Stony Brook, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States); Kennesaw State Univ., Kennesaw, GA (United States)
  5. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  7. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Report Number(s):
BNL-207900-2018-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 22; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
OSTI Identifier:
1462417