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Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles

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Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles. / Dippel, Ann Christin; Jensen, Kirsten M Ø; Tyrsted, Christoffer et al.

In: Acta Crystallographica Section A: Foundations and Advances, Vol. 72, No. 6, 2016, p. 645-650.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

Harvard

Dippel, AC, Jensen, KMØ, Tyrsted, C, Bremholm, M, Bøjesen, ED, Saha, D, Birgisson, S, Christensen, M, Billinge, SJL & Iversen, BB 2016, 'Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles', Acta Crystallographica Section A: Foundations and Advances, vol. 72, no. 6, pp. 645-650. https://doi.org/10.1107/S2053273316012675

APA

Dippel, A. C., Jensen, K. M. Ø., Tyrsted, C., Bremholm, M., Bøjesen, E. D., Saha, D., Birgisson, S., Christensen, M., Billinge, S. J. L., & Iversen, B. B. (2016). Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles. Acta Crystallographica Section A: Foundations and Advances, 72(6), 645-650. https://doi.org/10.1107/S2053273316012675

CBE

Dippel AC, Jensen KMØ, Tyrsted C, Bremholm M, Bøjesen ED, Saha D, Birgisson S, Christensen M, Billinge SJL, Iversen BB. 2016. Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles. Acta Crystallographica Section A: Foundations and Advances. 72(6):645-650. https://doi.org/10.1107/S2053273316012675

MLA

Dippel, Ann Christin et al. "Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles". Acta Crystallographica Section A: Foundations and Advances. 2016, 72(6). 645-650. https://doi.org/10.1107/S2053273316012675

Vancouver

Dippel AC, Jensen KMØ, Tyrsted C, Bremholm M, Bøjesen ED, Saha D et al. Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles. Acta Crystallographica Section A: Foundations and Advances. 2016;72(6):645-650. doi: 10.1107/S2053273316012675

Author

Dippel, Ann Christin ; Jensen, Kirsten M Ø ; Tyrsted, Christoffer et al. / Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles. In: Acta Crystallographica Section A: Foundations and Advances. 2016 ; Vol. 72, No. 6. pp. 645-650.

Bibtex

@article{0235da3fa7964d7794c3b25dec1f37cc,
title = "Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles",
abstract = "Varying atomic short-range order is correlated with the ratio of the monoclinic (m) to tetragonal (t) phase in ZrO2 nanoparticle formation by solvothermal methods. Reactions from Zr oxynitrate in supercritical methanol and Zr acetate in water (hydrothermal route) were studied in situ by X-ray total scattering. Irrespective of the Zr source and solvent, the structure of the precursor in solution consists of edge-shared tetramer chains. Upon heating, the nearest-neighbor Zr - O and Zr - Zr distances shorten initially while the medium-range connectivity is broken. Depending on the reaction conditions, the disordered intermediate transforms either rapidly into m-ZrO2, or more gradually into mixed m- and t-ZrO2 with a concurrent increase of the shortest Zr - Zr distance. In the hydrothermal case, the structural similarity of the amorphous intermediate and m-ZrO2 favors the formation of almost phase-pure m-ZrO2 nanoparticles with a size of 5nm, considerably smaller than the often-cited critical size below which the tetragonal is assumed to be favoured. Pair distribution function analysis thus unravels ZrO2 phase formation on the atomic scale and in this way provides a major step towards understanding polymorphism of ZrO2 beyond empirical approaches.The chemical path towards different polymorphs in the solvothermal synthesis of zirconia nanoparticles is decided by a complex interplay among reactants and applied conditions: at low temperature the structural similarity between the amorphous intermediate phase and monoclinic ZrO2 results in almost phase-purenm monoclinic ZrO2. Atomic scale pair distribution function analysis over the entire course of the reaction provides an understanding, and thereby control, of nanoparticle polymorphism.",
keywords = "nanoparticles, pair distribution function, polymorphism, solvothermal synthesis, zirconia",
author = "Dippel, {Ann Christin} and Jensen, {Kirsten M {\O}} and Christoffer Tyrsted and Martin Bremholm and B{\o}jesen, {Espen D.} and Dipankar Saha and Steinar Birgisson and Mogens Christensen and Billinge, {Simon J L} and Iversen, {Bo B.}",
year = "2016",
doi = "10.1107/S2053273316012675",
language = "English",
volume = "72",
pages = "645--650",
journal = "Acta Crystallographica Section A: Foundations and Advances",
issn = "0108-7673",
publisher = "John Wiley and Sons Inc.",
number = "6",

}

RIS

TY - JOUR

T1 - Towards atomistic understanding of polymorphism in the solvothermal synthesis of ZrO2 nanoparticles

AU - Dippel, Ann Christin

AU - Jensen, Kirsten M Ø

AU - Tyrsted, Christoffer

AU - Bremholm, Martin

AU - Bøjesen, Espen D.

AU - Saha, Dipankar

AU - Birgisson, Steinar

AU - Christensen, Mogens

AU - Billinge, Simon J L

AU - Iversen, Bo B.

PY - 2016

Y1 - 2016

N2 - Varying atomic short-range order is correlated with the ratio of the monoclinic (m) to tetragonal (t) phase in ZrO2 nanoparticle formation by solvothermal methods. Reactions from Zr oxynitrate in supercritical methanol and Zr acetate in water (hydrothermal route) were studied in situ by X-ray total scattering. Irrespective of the Zr source and solvent, the structure of the precursor in solution consists of edge-shared tetramer chains. Upon heating, the nearest-neighbor Zr - O and Zr - Zr distances shorten initially while the medium-range connectivity is broken. Depending on the reaction conditions, the disordered intermediate transforms either rapidly into m-ZrO2, or more gradually into mixed m- and t-ZrO2 with a concurrent increase of the shortest Zr - Zr distance. In the hydrothermal case, the structural similarity of the amorphous intermediate and m-ZrO2 favors the formation of almost phase-pure m-ZrO2 nanoparticles with a size of 5nm, considerably smaller than the often-cited critical size below which the tetragonal is assumed to be favoured. Pair distribution function analysis thus unravels ZrO2 phase formation on the atomic scale and in this way provides a major step towards understanding polymorphism of ZrO2 beyond empirical approaches.The chemical path towards different polymorphs in the solvothermal synthesis of zirconia nanoparticles is decided by a complex interplay among reactants and applied conditions: at low temperature the structural similarity between the amorphous intermediate phase and monoclinic ZrO2 results in almost phase-purenm monoclinic ZrO2. Atomic scale pair distribution function analysis over the entire course of the reaction provides an understanding, and thereby control, of nanoparticle polymorphism.

AB - Varying atomic short-range order is correlated with the ratio of the monoclinic (m) to tetragonal (t) phase in ZrO2 nanoparticle formation by solvothermal methods. Reactions from Zr oxynitrate in supercritical methanol and Zr acetate in water (hydrothermal route) were studied in situ by X-ray total scattering. Irrespective of the Zr source and solvent, the structure of the precursor in solution consists of edge-shared tetramer chains. Upon heating, the nearest-neighbor Zr - O and Zr - Zr distances shorten initially while the medium-range connectivity is broken. Depending on the reaction conditions, the disordered intermediate transforms either rapidly into m-ZrO2, or more gradually into mixed m- and t-ZrO2 with a concurrent increase of the shortest Zr - Zr distance. In the hydrothermal case, the structural similarity of the amorphous intermediate and m-ZrO2 favors the formation of almost phase-pure m-ZrO2 nanoparticles with a size of 5nm, considerably smaller than the often-cited critical size below which the tetragonal is assumed to be favoured. Pair distribution function analysis thus unravels ZrO2 phase formation on the atomic scale and in this way provides a major step towards understanding polymorphism of ZrO2 beyond empirical approaches.The chemical path towards different polymorphs in the solvothermal synthesis of zirconia nanoparticles is decided by a complex interplay among reactants and applied conditions: at low temperature the structural similarity between the amorphous intermediate phase and monoclinic ZrO2 results in almost phase-purenm monoclinic ZrO2. Atomic scale pair distribution function analysis over the entire course of the reaction provides an understanding, and thereby control, of nanoparticle polymorphism.

KW - nanoparticles

KW - pair distribution function

KW - polymorphism

KW - solvothermal synthesis

KW - zirconia

U2 - 10.1107/S2053273316012675

DO - 10.1107/S2053273316012675

M3 - Journal article

C2 - 27809203

AN - SCOPUS:84994236447

VL - 72

SP - 645

EP - 650

JO - Acta Crystallographica Section A: Foundations and Advances

JF - Acta Crystallographica Section A: Foundations and Advances

SN - 0108-7673

IS - 6

ER -