Structural modulation in potassium birnessite single crystals

Liliia D. Kulish; Pavan Nukala; Rick Scholtens; A. G.M. Uiterwijk; Ruben Hamming-Green; Graeme R. Blake

doi:10.1039/d0tc05396a

Structural modulation in potassium birnessite single crystals

Liliia D. Kulish^*, Pavan Nukala, Rick Scholtens, A. G.M. Uiterwijk, Ruben Hamming-Green, Graeme R. Blake

^*Corresponding author for this work

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Abstract

We report on the growth of single-crystal potassium birnessite (K_0.31MnO₂·0.41H₂O) and present both the average and local structural characterization of this frustrated magnetic system. Single crystals were obtained employing a flux growth method with a KNO₃/B₂O₃flux at 700 °C. Single-crystal X-ray diffraction revealed an average orthorhombic symmetry, with space groupCmcm. A combination of high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with atomic resolution energy dispersive X-ray spectroscopy (EDS) demonstrated the layered structure of potassium birnessite with manganese-containing planes well separated by layers of potassium atoms. MnO₆octahedra and the K/H₂O planes were clearly imagedviaintegrated differential phase contrast (iDPC) STEM. Furthermore, iDPC-STEM also revealed the existence of local domains with alternating contrast of the manganese oxide planes, most likely originating from charge ordering of Mn³⁺and Mn⁴⁺along thec-axis. These charge-ordered domains are clearly correlated with a reduction in thec-lattice parameter compared to the rest of the matrix. The insight gained from this work allows for a better understanding of the correlation between structure and magnetic properties.

Original language	English
Pages (from-to)	1370-1377
Number of pages	8
Journal	Journal of Materials Chemistry C
Volume	9
Issue number	4
DOIs	https://doi.org/10.1039/d0tc05396a
Publication status	Published - 28-Jan-2021

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@article{ed9e54ca0661496db663f9d8a652f146,

title = "Structural modulation in potassium birnessite single crystals",

abstract = "We report on the growth of single-crystal potassium birnessite (K0.31MnO2·0.41H2O) and present both the average and local structural characterization of this frustrated magnetic system. Single crystals were obtained employing a flux growth method with a KNO3/B2O3flux at 700 °C. Single-crystal X-ray diffraction revealed an average orthorhombic symmetry, with space groupCmcm. A combination of high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with atomic resolution energy dispersive X-ray spectroscopy (EDS) demonstrated the layered structure of potassium birnessite with manganese-containing planes well separated by layers of potassium atoms. MnO6octahedra and the K/H2O planes were clearly imagedviaintegrated differential phase contrast (iDPC) STEM. Furthermore, iDPC-STEM also revealed the existence of local domains with alternating contrast of the manganese oxide planes, most likely originating from charge ordering of Mn3+and Mn4+along thec-axis. These charge-ordered domains are clearly correlated with a reduction in thec-lattice parameter compared to the rest of the matrix. The insight gained from this work allows for a better understanding of the correlation between structure and magnetic properties.",

author = "Kulish, {Liliia D.} and Pavan Nukala and Rick Scholtens and Uiterwijk, {A. G.M.} and Ruben Hamming-Green and Blake, {Graeme R.}",

note = "Funding Information: This work was supported by the European Union's Horizon 2020 research and innovation program under a Marie Sklodowska-Curie Individual Fellowship, Grant Agreement No. 833550 and 794954. We thank Prof. Ronnie Hoekstra and Dr Harry Jonkman for valuable discussion and assistance with XPS measurements; Prof. Beatriz Noheda for insightful discussion and resource support; Dr V?clav Ocelik for assistance with the SEM images; Ing. Jacob Baas for technical support; Joshua Levinsky for constructive suggestions during the determination of the crystal structure; Jordi Antoja-Lleonart for valuable recommendations regarding error propagation calculation. Funding Information: This work was supported by the European Union{\textquoteright}s Horizon 2020 research and innovation program under a Marie Sklodowska-Curie Individual Fellowship, Grant Agreement No. 833550 and 794954. We thank Prof. Ronnie Hoekstra and Dr Harry Jonkman for valuable discussion and assistance with XPS measurements; Prof. Beatriz Noheda for insightful discussion and resource support; Dr V{\'a}clav Ocelik for assistance with the SEM images; Ing. Jacob Baas for technical support; Joshua Levinsky for constructive suggestions during the determination of the crystal structure; Jordi Antoja-Lleonart for valuable recommendations regarding error propagation calculation. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = jan,

day = "28",

doi = "10.1039/d0tc05396a",

language = "English",

volume = "9",

pages = "1370--1377",

journal = "Journal of Materials Chemistry C",

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publisher = "ROYAL SOC CHEMISTRY",

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T1 - Structural modulation in potassium birnessite single crystals

AU - Kulish, Liliia D.

AU - Nukala, Pavan

AU - Scholtens, Rick

AU - Uiterwijk, A. G.M.

AU - Hamming-Green, Ruben

AU - Blake, Graeme R.

N1 - Funding Information: This work was supported by the European Union's Horizon 2020 research and innovation program under a Marie Sklodowska-Curie Individual Fellowship, Grant Agreement No. 833550 and 794954. We thank Prof. Ronnie Hoekstra and Dr Harry Jonkman for valuable discussion and assistance with XPS measurements; Prof. Beatriz Noheda for insightful discussion and resource support; Dr V?clav Ocelik for assistance with the SEM images; Ing. Jacob Baas for technical support; Joshua Levinsky for constructive suggestions during the determination of the crystal structure; Jordi Antoja-Lleonart for valuable recommendations regarding error propagation calculation. Funding Information: This work was supported by the European Union’s Horizon 2020 research and innovation program under a Marie Sklodowska-Curie Individual Fellowship, Grant Agreement No. 833550 and 794954. We thank Prof. Ronnie Hoekstra and Dr Harry Jonkman for valuable discussion and assistance with XPS measurements; Prof. Beatriz Noheda for insightful discussion and resource support; Dr Václav Ocelik for assistance with the SEM images; Ing. Jacob Baas for technical support; Joshua Levinsky for constructive suggestions during the determination of the crystal structure; Jordi Antoja-Lleonart for valuable recommendations regarding error propagation calculation. Publisher Copyright: © The Royal Society of Chemistry 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/1/28

Y1 - 2021/1/28

N2 - We report on the growth of single-crystal potassium birnessite (K0.31MnO2·0.41H2O) and present both the average and local structural characterization of this frustrated magnetic system. Single crystals were obtained employing a flux growth method with a KNO3/B2O3flux at 700 °C. Single-crystal X-ray diffraction revealed an average orthorhombic symmetry, with space groupCmcm. A combination of high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with atomic resolution energy dispersive X-ray spectroscopy (EDS) demonstrated the layered structure of potassium birnessite with manganese-containing planes well separated by layers of potassium atoms. MnO6octahedra and the K/H2O planes were clearly imagedviaintegrated differential phase contrast (iDPC) STEM. Furthermore, iDPC-STEM also revealed the existence of local domains with alternating contrast of the manganese oxide planes, most likely originating from charge ordering of Mn3+and Mn4+along thec-axis. These charge-ordered domains are clearly correlated with a reduction in thec-lattice parameter compared to the rest of the matrix. The insight gained from this work allows for a better understanding of the correlation between structure and magnetic properties.

AB - We report on the growth of single-crystal potassium birnessite (K0.31MnO2·0.41H2O) and present both the average and local structural characterization of this frustrated magnetic system. Single crystals were obtained employing a flux growth method with a KNO3/B2O3flux at 700 °C. Single-crystal X-ray diffraction revealed an average orthorhombic symmetry, with space groupCmcm. A combination of high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with atomic resolution energy dispersive X-ray spectroscopy (EDS) demonstrated the layered structure of potassium birnessite with manganese-containing planes well separated by layers of potassium atoms. MnO6octahedra and the K/H2O planes were clearly imagedviaintegrated differential phase contrast (iDPC) STEM. Furthermore, iDPC-STEM also revealed the existence of local domains with alternating contrast of the manganese oxide planes, most likely originating from charge ordering of Mn3+and Mn4+along thec-axis. These charge-ordered domains are clearly correlated with a reduction in thec-lattice parameter compared to the rest of the matrix. The insight gained from this work allows for a better understanding of the correlation between structure and magnetic properties.

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U2 - 10.1039/d0tc05396a

DO - 10.1039/d0tc05396a

M3 - Article

AN - SCOPUS:85100518808

SN - 2050-7534

VL - 9

SP - 1370

EP - 1377

JO - Journal of Materials Chemistry C

JF - Journal of Materials Chemistry C

IS - 4

ER -

Structural modulation in potassium birnessite single crystals

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CSD 2041937: Experimental Crystal Structure Determination

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Structural modulation in potassium birnessite single crystals

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CSD 2041937: Experimental Crystal Structure Determination

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