High temperature hydrothermal synthesis of rare-earth titanates: synthesis and structure of RE5Ti4O15(OH) (RE = La, Er), Sm3TiO5(OH)3, RE5Ti2O11(OH) (RE = Tm–Lu) and Ce2 Ti4O11

Fulle, Kyle; Sanjeewa, Liurukara D.; McMillen, Colin D.; Kolis, Joseph W.

doi:10.1039/c7dt04810f

High temperature hydrothermal synthesis of rare-earth titanates: synthesis and structure of RE₅Ti₄O₁₅(OH) (RE = La, Er), Sm₃TiO₅(OH)₃, RE₅Ti₂O₁₁(OH) (RE = Tm–Lu) and Ce₂ Ti₄O₁₁

Journal Article · Wed May 02 00:00:00 EDT 2018 · Dalton Transactions

DOI:https://doi.org/10.1039/c7dt04810f· OSTI ID:1596442

Fulle, Kyle ^[1]; Sanjeewa, Liurukara D. ^[2]; ^[2]; Kolis, Joseph W. ^[2]

Clemson Univ., SC (United States). Center for Optical Materials Science and Engineering Technologies (COMSET); Clemson University Department of Chemistry
Clemson Univ., SC (United States). Center for Optical Materials Science and Engineering Technologies (COMSET)

Reactions of rare-earth oxides with TiO₂ were performed in high temperature (650–700 °C) hydrothermal fluids. Two different mineralizer fluids were examined, 20 M KOH and 30 M CsF, and their respective products analyzed. When concentrated KOH fluids were used, single crystals of a variety of new OH^- containing species were isolated and structurally characterized: RE₅Ti₄O₁₅(OH) (RE = La, Er) I, Sm₃TiO₅(OH)₃II and RE₅Ti₂O₁₁(OH) (RE = Tm–Lu) III. La₅Ti₄O₁₅(OH) I crystallizes in the orthorhombic space group Pnnm with unit cell dimensions of a = 30.5152(12) Å, b = 5.5832(2) Å, c = 7.7590(3) Å and V = 1321.92(9) Å³, Z = 4. Sm₃TiO₅(OH)₃II crystallizes in the monoclinic space group P21/m with unit cell parameters of a = 5.6066(2) Å, b = 10.4622(4) Å, c = 6.1258(2) Å and β = 104.7390(10)°, V = 347.50(2) Å3, Z = 2. Lu5Ti2O11(OH) III crystallizes in the monoclinic space group C2/m with unit cell dimensions of a = 12.1252(9) Å, b = 5.8243(4) Å, c = 7.0407(5) Å, β = 106.939(3)° and V = 475.65(6) Å3, Z = 2. When concentrated fluoride solutions are used, mostly RE₂Ti₂O₇ type compounds were isolated in either cubic or monoclinic phases. In the case of cerium, Ce2Ti4O11IV was isolated that crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 13.6875(7) Å, b = 5.0955(3) Å, c = 12.8592(7) Å, β = 108.964(2)° and V = 848.18(8) Å³, Z = 4. The synthesis, structural characterization, and supporting characterization are reported for all compounds. The work highlights the complementary nature of hydroxide and fluoride fluids in studying the reactivity of refractory oxides.

View Accepted Manuscript (DOE)

Research Organization:: Clemson Univ., SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0014271

OSTI ID:: 1596442

Alternate ID(s):: OSTI ID: 1539921
OSTI ID: 1435657

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 19 Vol. 47; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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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) Sanjeewa, Liurukara D.; Fulle, Kyle; McMillen, Colin D. Dalton Transactions, Vol. 48, Issue 22 https://doi.org/10.1039/c9dt00059c	journal	January 2019

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36 MATERIALS SCIENCE
Crystal Growth
Hydrothermal
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Titanates

CSD 1886581: Experimental Crystal Structure Determination Fulle, Kyle; Sanjeewa, Liurukara D.; McMillena, Colin D. https://doi.org/10.25505/fiz.icsd.cc21b4g0 The current record is supplemented by this dataset	dataset	January 2018
CSD 1886582: Experimental Crystal Structure Determination Fulle, Kyle; Sanjeewa, Liurukara D.; McMillena, Colin D. https://doi.org/10.25505/fiz.icsd.cc21b4h1 The current record is supplemented by this dataset	dataset	January 2018
CSD 1886583: Experimental Crystal Structure Determination Fulle, Kyle; Sanjeewa, Liurukara D.; McMillena, Colin D. https://doi.org/10.25505/fiz.icsd.cc21b4j2 The current record is supplemented by this dataset	dataset	January 2018
CSD 1886584: Experimental Crystal Structure Determination Fulle, Kyle; Sanjeewa, Liurukara D.; McMillena, Colin D. https://doi.org/10.25505/fiz.icsd.cc21b4k3 The current record is supplemented by this dataset	dataset	January 2018
CSD 1886585: Experimental Crystal Structure Determination Fulle, Kyle; Sanjeewa, Liurukara D.; McMillena, Colin D. https://doi.org/10.25505/fiz.icsd.cc21b4l4 The current record is supplemented by this dataset	dataset	January 2018