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Title: Denticity and Mobility of the Carbonate Groups in AMCO 3 F Fluorocarbonates: A Study on KMnCO 3 F and High Temperature KCaCO 3 F Polymorph

Abstract

We report on a thorough structural study on two members of layered fluorocarbonates KMCO3F (M = Ca, Mn). The Ca-based member demonstrates a phase transition at ~320 °C, evidenced for the first time. The crystal structure of the high temperature phase (HT-KCaCO3F) was solved using neutron powder diffraction. A new Mn-based phase KMnCO3F was synthesized, and its crystal structure was solved from electron diffraction tomography data and refined from a combination of X-ray synchrotron and neutron powder diffraction. In contrast to other members of the fluorocarbonate family, the carbonate groups in the KMnCO3F and HT-KCaCO3F structures are not fixed to two distinct orientations corresponding to mono- and bidentate coordinations of the M cation. In KMnCO3F, the carbonate group can be considered as nearly “monodentate”, forming one short (2.14 Å) and one long (3.01 Å) Mn–O contact. This topology provides more flexibility to the MCO3 layer and enables diminishing the mismatch between the MCO3 and KF layers. This conclusion is corroborated by the HT-KCaCO3F structure, in which the carbonate groups can additionally be tilted away from the layer plane thus relieving the strain arising from geometrical mismatch between the layers. The correlation between denticity of the carbonate groups, their mobility, andmore » cation size variance is discussed. KMnCO3 orders antiferromagnetically below TN = 40 K.« less

Authors:
 [1];  [2];  [3];  [1];  [2]; ORCiD logo [4]
  1. UMR 8260 “Chimie du solide et énergie”, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France; Sorbonne Universités—UPMC Univ Paris 06, 4 Place Jussieu, F-75005 Paris, France; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France
  2. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France; Laboratoire de Réactivité et Chimie des Solides, UMR CNRS 7314, 33 Rue Saint Leu, 80039 Amiens Cedex, France; ALISTORE-European Research Institute, FR CNRS 3104, 80039 Amiens, France
  3. Laboratory for Neutron Scattering, Paul Scherrer Institut, CH-5232 Villigen, Switzerland
  4. Center for Electrochemical Energy Storage, Skolkovo Institute of Science and Technology, Nobel Street 3, 143026 Moscow, Russia
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1410124
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 56; Journal Issue: 21
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rousse, Gwenaelle, Ahouari, Hania, Pomjakushin, Vladimir, Tarascon, Jean-Marie, Recham, Nadir, and Abakumov, Artem M. Denticity and Mobility of the Carbonate Groups in AMCO 3 F Fluorocarbonates: A Study on KMnCO 3 F and High Temperature KCaCO 3 F Polymorph. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b01926.
Rousse, Gwenaelle, Ahouari, Hania, Pomjakushin, Vladimir, Tarascon, Jean-Marie, Recham, Nadir, & Abakumov, Artem M. Denticity and Mobility of the Carbonate Groups in AMCO 3 F Fluorocarbonates: A Study on KMnCO 3 F and High Temperature KCaCO 3 F Polymorph. United States. doi:10.1021/acs.inorgchem.7b01926.
Rousse, Gwenaelle, Ahouari, Hania, Pomjakushin, Vladimir, Tarascon, Jean-Marie, Recham, Nadir, and Abakumov, Artem M. Wed . "Denticity and Mobility of the Carbonate Groups in AMCO 3 F Fluorocarbonates: A Study on KMnCO 3 F and High Temperature KCaCO 3 F Polymorph". United States. doi:10.1021/acs.inorgchem.7b01926.
@article{osti_1410124,
title = {Denticity and Mobility of the Carbonate Groups in AMCO 3 F Fluorocarbonates: A Study on KMnCO 3 F and High Temperature KCaCO 3 F Polymorph},
author = {Rousse, Gwenaelle and Ahouari, Hania and Pomjakushin, Vladimir and Tarascon, Jean-Marie and Recham, Nadir and Abakumov, Artem M.},
abstractNote = {We report on a thorough structural study on two members of layered fluorocarbonates KMCO3F (M = Ca, Mn). The Ca-based member demonstrates a phase transition at ~320 °C, evidenced for the first time. The crystal structure of the high temperature phase (HT-KCaCO3F) was solved using neutron powder diffraction. A new Mn-based phase KMnCO3F was synthesized, and its crystal structure was solved from electron diffraction tomography data and refined from a combination of X-ray synchrotron and neutron powder diffraction. In contrast to other members of the fluorocarbonate family, the carbonate groups in the KMnCO3F and HT-KCaCO3F structures are not fixed to two distinct orientations corresponding to mono- and bidentate coordinations of the M cation. In KMnCO3F, the carbonate group can be considered as nearly “monodentate”, forming one short (2.14 Å) and one long (3.01 Å) Mn–O contact. This topology provides more flexibility to the MCO3 layer and enables diminishing the mismatch between the MCO3 and KF layers. This conclusion is corroborated by the HT-KCaCO3F structure, in which the carbonate groups can additionally be tilted away from the layer plane thus relieving the strain arising from geometrical mismatch between the layers. The correlation between denticity of the carbonate groups, their mobility, and cation size variance is discussed. KMnCO3 orders antiferromagnetically below TN = 40 K.},
doi = {10.1021/acs.inorgchem.7b01926},
journal = {Inorganic Chemistry},
number = 21,
volume = 56,
place = {United States},
year = {Wed Oct 18 00:00:00 EDT 2017},
month = {Wed Oct 18 00:00:00 EDT 2017}
}