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Title: Hydrothermal synthesis and structural characterization of several complex rare earth tantalates: Ln 2 TaO 5 (OH) (Ln = La, Pr) and Ln 3 Ta 2 O 9 (OH) (Ln = Pr, Nd)

Abstract

Reactions are reported of early rare earth oxides, RE 2O 3 (RE = La, Pr, Nd) with Ta 2O 5 under hydrothermal conditions (650 °C, 1.5 kbar) in concentrated aqueous hydroxide (20–30 M KOH) as a mineralizer. Under various stoichiometries several members of two new structure types were isolated, Ln 2TaO 5(OH) (Ln = La, Pr) and Ln 3Ta 2O 9(OH) (Ln = Pr, Nd). The analogous niobate La 2NbO 5(OH) was also obtained. Both structure types were characterized by single crystal X-ray diffraction and contain pentavalent tantalatum oxide octahedra and complex rare earth oxide frameworks. The Ln 2TaO 5(OH) structure type contains Ln–O 8 and Ln–O 9 building blocks and TaO 6 octahedra in a 3-D framework. It contains a 3-D rare earth oxide framework formed by from zig-zag chains of rare earth oxides linking sheets of rare earth oxides. The tantalates form edge-shared Ta 2O 10 dimers occupying gaps in the rare earth oxide frameworks. The structure of Ln 3Ta 2O 9(OH) contains two types of 2-D rare earth oxide slabs built of seven and eight coordinate rare earth metals. The tantalate units form 2-D slabs through a multiple corner-sharing scheme of TaO 6 octahedra. The Ln 3Tamore » 2O 9(OH) structure type has an interesting close structural relationship to the previously reported rare earth titanate La 5Ti 4O 15(OH), which is discussed. The presence of hydroxide in the lattice is confirmed by IR spectroscopy and the H atom locations are assigned unambiguously using bond valence sums.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [1]
  1. Clemson Univ., SC (United States). Center for Optical Materials Science and Engineering Technologies (COMSET)
Publication Date:
Research Org.:
Clemson Univ., SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1596441
Alternate Identifier(s):
OSTI ID: 1511501
Grant/Contract Number:  
[SC0014271]
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
[ Journal Volume: 48; Journal Issue: 22]; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Hydrothermal Crystal growth; Rare earth; Tantalates

Citation Formats

Sanjeewa, Liurukara D., Fulle, Kyle, McMillen, Colin D., and Kolis, Joseph W. Hydrothermal synthesis and structural characterization of several complex rare earth tantalates: Ln2 TaO5 (OH) (Ln = La, Pr) and Ln3 Ta2 O9 (OH) (Ln = Pr, Nd). United States: N. p., 2019. Web. doi:10.1039/c9dt00059c.
Sanjeewa, Liurukara D., Fulle, Kyle, McMillen, Colin D., & Kolis, Joseph W. Hydrothermal synthesis and structural characterization of several complex rare earth tantalates: Ln2 TaO5 (OH) (Ln = La, Pr) and Ln3 Ta2 O9 (OH) (Ln = Pr, Nd). United States. doi:10.1039/c9dt00059c.
Sanjeewa, Liurukara D., Fulle, Kyle, McMillen, Colin D., and Kolis, Joseph W. Wed . "Hydrothermal synthesis and structural characterization of several complex rare earth tantalates: Ln2 TaO5 (OH) (Ln = La, Pr) and Ln3 Ta2 O9 (OH) (Ln = Pr, Nd)". United States. doi:10.1039/c9dt00059c.
@article{osti_1596441,
title = {Hydrothermal synthesis and structural characterization of several complex rare earth tantalates: Ln2 TaO5 (OH) (Ln = La, Pr) and Ln3 Ta2 O9 (OH) (Ln = Pr, Nd)},
author = {Sanjeewa, Liurukara D. and Fulle, Kyle and McMillen, Colin D. and Kolis, Joseph W.},
abstractNote = {Reactions are reported of early rare earth oxides, RE2O3 (RE = La, Pr, Nd) with Ta2O5 under hydrothermal conditions (650 °C, 1.5 kbar) in concentrated aqueous hydroxide (20–30 M KOH) as a mineralizer. Under various stoichiometries several members of two new structure types were isolated, Ln2TaO5(OH) (Ln = La, Pr) and Ln3Ta2O9(OH) (Ln = Pr, Nd). The analogous niobate La2NbO5(OH) was also obtained. Both structure types were characterized by single crystal X-ray diffraction and contain pentavalent tantalatum oxide octahedra and complex rare earth oxide frameworks. The Ln2TaO5(OH) structure type contains Ln–O8 and Ln–O9 building blocks and TaO6 octahedra in a 3-D framework. It contains a 3-D rare earth oxide framework formed by from zig-zag chains of rare earth oxides linking sheets of rare earth oxides. The tantalates form edge-shared Ta2O10 dimers occupying gaps in the rare earth oxide frameworks. The structure of Ln3Ta2O9(OH) contains two types of 2-D rare earth oxide slabs built of seven and eight coordinate rare earth metals. The tantalate units form 2-D slabs through a multiple corner-sharing scheme of TaO6 octahedra. The Ln3Ta2O9(OH) structure type has an interesting close structural relationship to the previously reported rare earth titanate La5Ti4O15(OH), which is discussed. The presence of hydroxide in the lattice is confirmed by IR spectroscopy and the H atom locations are assigned unambiguously using bond valence sums.},
doi = {10.1039/c9dt00059c},
journal = {Dalton Transactions},
number = [22],
volume = [48],
place = {United States},
year = {2019},
month = {5}
}

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    Works referencing / citing this record:

    Materials Discovery by Flux Crystal Growth: Quaternary and Higher Order Oxides
    journal, January 2012

    • Bugaris, Daniel E.; zur Loye, Hans-Conrad
    • Angewandte Chemie International Edition, Vol. 51, Issue 16
    • DOI: 10.1002/anie.201102676

    Über Oxotantalate der Lanthanide des Formeltyps MTaO4 (M = La - Nd, Sm - Lu)
    journal, September 2005

    • Hartenbach, Ingo; Lissner, Falk; Nikelski, Tanja
    • Zeitschrift für anorganische und allgemeine Chemie, Vol. 631, Issue 12
    • DOI: 10.1002/zaac.200500278

    The phase diagram, LiOH-Ta2 O5-H2O and the hydrothermal synthesis of LiTaO3 and LiNbO3
    journal, April 1976


    The structure of LaTaO4 at 300°C by neutron powder profile analysis
    journal, February 1981


    Phase changes and lattice distortion in fluorite-related phases of R3TaO7 (3R2O3·Ta2O5, R=rare earth)
    journal, November 1987

    • Yokogawa, Yoshiyuki; Yoshimura, Masahiro; Sōmiya, Shigeyuki
    • Materials Research Bulletin, Vol. 22, Issue 11
    • DOI: 10.1016/0025-5408(87)90209-1

    Order-disorder in R3TaO7 (R=rare earth) phases
    journal, September 1988


    Luminescence of materials based on LuTaO4
    journal, July 1994


    The crystal chemistry of L-Ta2O5 and related structures
    journal, November 2005


    Distribution, structures and nonlinear properties of noncentrosymmetric niobates and tantalates
    journal, April 2006


    Materials discovery by crystal growth: Lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt) from molten alkali metal hydroxides
    journal, July 2009

    • Mugavero, Samuel J.; Gemmill, William R.; Roof, Irina P.
    • Journal of Solid State Chemistry, Vol. 182, Issue 7
    • DOI: 10.1016/j.jssc.2009.05.006

    Hydrothermal crystal growth of the potassium niobate and potassium tantalate family of crystals
    journal, November 2010

    • Mann, Matthew; Jackson, Summer; Kolis, Joseph
    • Journal of Solid State Chemistry, Vol. 183, Issue 11
    • DOI: 10.1016/j.jssc.2010.09.011

    Synthesis, properties and phase transitions of pyrochlore- and fluorite-like Ln2RMO7 (Ln=Sm, Ho; R=Lu, Sc; M=Nb, Ta)
    journal, January 2014


    Hydrothermal Chemistry and Growth of Fergusonite-type RENbO 4 (RE = La–Lu, Y) Single Crystals and New Niobate Hydroxides
    journal, August 2016

    • Fulle, Kyle; McMillen, Colin D.; Sanjeewa, Liurukara D.
    • Crystal Growth & Design, Vol. 16, Issue 9
    • DOI: 10.1021/acs.cgd.6b00466

    One-Pot Hydrothermal Synthesis of Tb III 13 (GeO 4 ) 6 O 7 (OH) and K 2 Tb IV Ge 2 O 7 : Preparation of a Stable Terbium(4+) Complex
    journal, May 2017


    Inorganic Materials as Catalysts for Photochemical Splitting of Water
    journal, January 2008


    Crystal Growth of a New Series of Complex Niobates, LnKNaNbO 5 (Ln = La, Pr, Nd, Sm, Eu, Gd, and Tb): Structural Properties and Photoluminescence
    journal, May 2009

    • Roof, Irina P.; Jagau, Thomas-C.; Zeier, Wolfgang G.
    • Chemistry of Materials, Vol. 21, Issue 9
    • DOI: 10.1021/cm9003245

    Unique LaTaO 4 Polymorph for Multiple Energy Applications
    journal, October 2009

    • Nyman, May; Rodriguez, Mark A.; Rohwer, Lauren E. S.
    • Chemistry of Materials, Vol. 21, Issue 19
    • DOI: 10.1021/cm9020645

    EuKNaTaO 5 : Crystal Growth, Structure and Photoluminescence Property
    journal, April 2009

    • Roof, Irina P.; Smith, Mark D.; Park, Sangmoon
    • Journal of the American Chemical Society, Vol. 131, Issue 12
    • DOI: 10.1021/ja8100769

    Photocatalytic Property and Electronic Structure of Lanthanide Tantalates, LnTaO 4 (Ln = La, Ce, Pr, Nd, and Sm)
    journal, April 2001

    • Machida, Masato; Murakami, Shunsuke; Kijima, Tsuyoshi
    • The Journal of Physical Chemistry B, Vol. 105, Issue 16
    • DOI: 10.1021/jp004297z

    Photocatalytic Water Splitting into H 2 and O 2 over R 3 TaO 7 and R 3 NbO 7 (R = Y, Yb, Gd, La):  Effect of Crystal Structure on Photocatalytic Activity
    journal, January 2004

    • Abe, Ryu; Higashi, Masanobu; Zou, Zhigang
    • The Journal of Physical Chemistry B, Vol. 108, Issue 3
    • DOI: 10.1021/jp036300v

    Enhancement of the dielectric constant of Ta2O5through substitution with TiO2
    journal, September 1995

    • Cava, R. F.; Peck, W. F.; Krajewski, J. J.
    • Nature, Vol. 377, Issue 6546
    • DOI: 10.1038/377215a0

    Dielectric materials for applications in microwave communications
    journal, January 2001

    • Cava, R. J.
    • Journal of Materials Chemistry, Vol. 11, Issue 1
    • DOI: 10.1039/b003681l

    Thermochemical insights into refractory ceramic materials based on oxides with large tetravalent cations
    journal, January 2005

    • Navrotsky, Alexandra
    • Journal of Materials Chemistry, Vol. 15, Issue 19
    • DOI: 10.1039/b417143h

    Bulk single crystal growth from hydrothermal solutions
    journal, July 2012


    Proton-Conducting Oxides
    journal, August 2003


    On the Structural and Luminescent Properties of the Mʹ LnTaO[sub 4] Rare Earth Tantalates
    journal, January 1983

    • Brixner, L. H.
    • Journal of The Electrochemical Society, Vol. 130, Issue 12
    • DOI: 10.1149/1.2119609