skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Chlorine-free, monolithic lanthanide series rare earth oxide aerogels via epoxide-assisted sol-gel method

Abstract

Synthesis of chlorine-free, rare earth oxide aerogels from the lanthanide series was achieved using a modified epoxide-assisted sol-gel method. An ethanolic solution of the hydrated metal nitrate, propylene oxide, and ammonium carbonate was found to gel upon heating to 333 K. Critical point drying of the wet gel in CO2 yielded monolithic aerogels. Most of the aerogels were amorphous as-prepared, but became nano-crystalline after calcination at 923 K in air. The aerogels had high surface areas (up to 150 m2/g), low densities (40–225 mg/cm3), and were photoluminescent.

Authors:
 [1];  [2];  [2];  [2];  [1];  [3];  [3];  [1];  [2]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Bremen (Germany)
  3. Univ. of Aveiro (Portugal)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); German Science Foundation (DFG); Fraunhofer Institute for Manufacturing Technology and Advanced Materials
OSTI Identifier:
1548325
Report Number(s):
LLNL-JRNL-782169
Journal ID: ISSN 0928-0707; 976425
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Sol-Gel Science and Technology
Additional Journal Information:
Journal Volume: 89; Journal Issue: 1; Journal ID: ISSN 0928-0707
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; rare earth oxide; aerogel; sol-gel; monolith; catalyst; photoluminescence; Rietveld refinement

Citation Formats

Worsley, M. A., Ilsemann, J., Gesing, Th. M., Zielasek, V., Nelson, A. J., Ferreira, R. A. S., Carlos, L. D., Gash, A. E., and Bäumer, M. Chlorine-free, monolithic lanthanide series rare earth oxide aerogels via epoxide-assisted sol-gel method. United States: N. p., 2018. Web. doi:10.1007/s10971-018-4811-y.
Worsley, M. A., Ilsemann, J., Gesing, Th. M., Zielasek, V., Nelson, A. J., Ferreira, R. A. S., Carlos, L. D., Gash, A. E., & Bäumer, M. Chlorine-free, monolithic lanthanide series rare earth oxide aerogels via epoxide-assisted sol-gel method. United States. doi:10.1007/s10971-018-4811-y.
Worsley, M. A., Ilsemann, J., Gesing, Th. M., Zielasek, V., Nelson, A. J., Ferreira, R. A. S., Carlos, L. D., Gash, A. E., and Bäumer, M. Fri . "Chlorine-free, monolithic lanthanide series rare earth oxide aerogels via epoxide-assisted sol-gel method". United States. doi:10.1007/s10971-018-4811-y. https://www.osti.gov/servlets/purl/1548325.
@article{osti_1548325,
title = {Chlorine-free, monolithic lanthanide series rare earth oxide aerogels via epoxide-assisted sol-gel method},
author = {Worsley, M. A. and Ilsemann, J. and Gesing, Th. M. and Zielasek, V. and Nelson, A. J. and Ferreira, R. A. S. and Carlos, L. D. and Gash, A. E. and Bäumer, M.},
abstractNote = {Synthesis of chlorine-free, rare earth oxide aerogels from the lanthanide series was achieved using a modified epoxide-assisted sol-gel method. An ethanolic solution of the hydrated metal nitrate, propylene oxide, and ammonium carbonate was found to gel upon heating to 333 K. Critical point drying of the wet gel in CO2 yielded monolithic aerogels. Most of the aerogels were amorphous as-prepared, but became nano-crystalline after calcination at 923 K in air. The aerogels had high surface areas (up to 150 m2/g), low densities (40–225 mg/cm3), and were photoluminescent.},
doi = {10.1007/s10971-018-4811-y},
journal = {Journal of Sol-Gel Science and Technology},
number = 1,
volume = 89,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Catalysis by Doped Oxides
journal, December 2012

  • McFarland, Eric W.; Metiu, Horia
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300418s

Rare Earth Oxide Coating of the Walls of SBA-15
journal, January 2002

  • Sauer, J.; Marlow, F.; Spliethoff, B.
  • Chemistry of Materials, Vol. 14, Issue 1
  • DOI: 10.1021/cm0111377

Low-Temperature Destruction of Chlorinated Hydrocarbons over Lanthanide Oxide Based Catalysts
journal, December 2002

  • Van der Avert, Pieter; Weckhuysen, Bert M.
  • Angewandte Chemie International Edition, Vol. 41, Issue 24
  • DOI: 10.1002/anie.200290030

Nanostructured Praseodymium Oxide:  Preparation, Structure, and Catalytic Properties
journal, February 2008

  • Borchert, Yulia; Sonström, Patrick; Wilhelm, Michaela
  • The Journal of Physical Chemistry C, Vol. 112, Issue 8
  • DOI: 10.1021/jp0768524

Structural Characteristics and Catalytic Activity of Nanocrystalline Ceria−Praseodymia Solid Solutions
journal, August 2009

  • Reddy, Benjaram M.; Thrimurthulu, Gode; Katta, Lakshmi
  • The Journal of Physical Chemistry C, Vol. 113, Issue 36
  • DOI: 10.1021/jp903644y

Synthesis and characterization of monolithic Gd2O3 aerogels
journal, September 2008


A new route to three-dimensionally well-ordered macroporous rare-earth oxides
journal, January 2001

  • Zhang, Yugen; Lei, Zhibin; Li, Jianmin
  • New Journal of Chemistry, Vol. 25, Issue 9
  • DOI: 10.1039/b104215g

Synthesis of lanthanide and lanthanide-silicate aerogels
journal, January 1994

  • Tillotson, T. M.; Sunderland, W. E.; Thomas, I. M.
  • Journal of Sol-Gel Science and Technology, Vol. 1, Issue 3
  • DOI: 10.1007/BF00486167

A sol–gel methodology for the preparation of lanthanide-oxide aerogels: preparation and characterization
journal, August 2012

  • Clapsaddle, Brady J.; Neumann, Björn; Wittstock, Arne
  • Journal of Sol-Gel Science and Technology, Vol. 64, Issue 2
  • DOI: 10.1007/s10971-012-2868-6

Influence of chlorine poisoning of copper/alumina catalyst on the selective hydrogenation of crotonaldehyde
journal, March 1994

  • Hutchings, Graham J.; King, Frank; Okoye, Ifedi P.
  • Catalysis Letters, Vol. 23, Issue 1-2
  • DOI: 10.1007/BF00812140

Chlorine-Containing compounds as copper catalyst poisons
journal, September 1982

  • Heldal, J. A.; Mørk, P. C.
  • Journal of the American Oil Chemists' Society, Vol. 59, Issue 9
  • DOI: 10.1007/BF02636051

Chlorine–nickel interactions in gas phase catalytic hydrodechlorination: catalyst deactivation and the nature of reactive hydrogen
journal, January 1999

  • Shin, Eun-Jae; Spiller, Andreas; Tavoularis, George
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 13
  • DOI: 10.1039/a902345c

Use of Epoxides in the Sol−Gel Synthesis of Porous Iron(III) Oxide Monoliths from Fe(III) Salts
journal, March 2001

  • Gash, Alexander E.; Tillotson, Thomas M.; Satcher, Joe H.
  • Chemistry of Materials, Vol. 13, Issue 3
  • DOI: 10.1021/cm0007611

Strong Akaganeite Aerogel Monoliths Using Epoxides:  Synthesis and Characterization
journal, August 2003

  • Gash, Alexander E.; Satcher, Joe H.; Simpson, Randall L.
  • Chemistry of Materials, Vol. 15, Issue 17, p. 3268-3275
  • DOI: 10.1021/cm034211p

Synthesis of High-Surface-Area Alumina Aerogels without the Use of Alkoxide Precursors
journal, January 2005

  • Baumann, Theodore F.; Gash, Alexander E.; Chinn, Sarah C.
  • Chemistry of Materials, Vol. 17, Issue 2, p. 395-401
  • DOI: 10.1021/cm048800m

Synthesis of high porosity, monolithic alumina aerogels
journal, June 2001


Structural and spectroscopic comparison between polycrystalline, nanocrystalline and quantum dot visible light photo-catalyst Bi 2 WO 6
journal, October 2017


Etude par diffraction neutronique des structures de haute temperature de La2O3 et Nd2O3
journal, March 1979


Structure properties and magnetic susceptibility of diluted magnetic semiconductor Y2−xHoxO3
journal, March 1995


The structure characteristics of the diluted magnetic semiconductor Y 2−x Dy x O 3
journal, December 1993


Structural study of Nd oxidation by means of in-situ synchrotron X-ray diffraction (400≤T≤700°C)
journal, April 2014


Shock-induced phase transition of M2O3 (M = Sc, Y, Sm, Gd, and In)-type compounds
journal, December 1990


Reversible B-type - A-type transition of Sm2O3 under high pressure
journal, September 1989


Refinement of atomic positions in bixbyite oxides using perturbed angular correlation spectroscopy
journal, April 1993

  • Bartos, A.; Lieb, K. P.; Uhrmacher, M.
  • Acta Crystallographica Section B Structural Science, Vol. 49, Issue 2
  • DOI: 10.1107/S0108768192007742

Structural and vibrational study of C-type doped rare earth sesquioxide Yb2−xCoxO3
journal, June 2009


Synthesis, structure and magnetic properties of the Lu2O3–CoO mixed system
journal, October 2010


Ordered intermediate phases in the system CeO2Ce2O3
journal, March 1955


Crystal growth of ytterbium dihydride and the phase relations in the Yb-H system
journal, October 1983


The crystal structure refinement and magnetic susceptibility study of La2−xErxO3
journal, July 2003


An X-ray diffraction and magnetic susceptibility study of TmxY2−xO3
journal, April 2000


Die Gitterkonstanten der C-Formen der Oxyde der seltenen Erdmetalle
journal, May 1939

  • Bommer, Heinrich
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 241, Issue 2-3
  • DOI: 10.1002/zaac.19392410215

Refinement of the Nd 2 O 3 structure and determination of the neutron scattering length of neodymium
journal, November 1975

  • Boucherle, J. X.; Schweizer, J.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 31, Issue 11
  • DOI: 10.1107/S0567740875008746

Etude de couches minces de sesquioxyde de samarium type B par microscopie et diffraction électroniques
journal, January 1971

  • Boulesteix, C.; Pardo, B.; Caro, P. E.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 1
  • DOI: 10.1107/S0567740871001924

Comparison of structural and luminescence properties of Dy2O3 nanopowders synthesized by co-precipitation and green combustion routes
journal, July 2014


Structural and phase dependent thermo and photoluminescent properties of Dy(OH)3 and Dy2O3 nanorods
journal, August 2012


An Energy-Dispersive X-Ray Diffraction Study of Monoclinic Eu2O3 under Pressure
journal, August 1994

  • Chen, G.; Peterson, J. R.; Brister, K. E.
  • Journal of Solid State Chemistry, Vol. 111, Issue 2
  • DOI: 10.1006/jssc.1994.1250

Polymorphic Modifications of Pm2O3
journal, August 1972


The Crystal Structure of Monoclinic Sm 2 0 2
journal, June 1957


Comparative structural and photoluminescent study of Eu3+-doped La2O3 and La(OH)3 nanocrystalline powders
journal, February 2014

  • Đorđević, Vesna; Antić, Željka; Nikolić, Marko G.
  • Journal of Physics and Chemistry of Solids, Vol. 75, Issue 2
  • DOI: 10.1016/j.jpcs.2013.10.004

Refinement of the Nd 2 O 3 and Nd 2 O 2 S structures at 4 K
journal, January 1982

  • Faucher, M.; Pannetier, J.; Charreire, Y.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 1
  • DOI: 10.1107/S056774088200288X

A new form of La2O3
journal, April 1969


The formation of rare earth oxides far from equilibrium
journal, February 1986


Raman spectra of lanthanide sesquioxide single crystals: Correlation between A and B-type structures
journal, July 1981


The crystal structure of the low-temperature A-type modification of Pr2O3 from X-ray powder and electron single crystal diffraction
journal, January 1995


Thermal Expansion of CeO2, Ho2O3, and Lu2O3 from 100o to 300oK by an X-Ray Method
journal, December 1970


Structural Investigations of Lu 2 O 3 as Single Crystal and Polycrystalline Transparent Ceramic
journal, May 2014

  • Guzik, Malgorzata; Pejchal, Jan; Yoshikawa, Akira
  • Crystal Growth & Design, Vol. 14, Issue 7
  • DOI: 10.1021/cg500225v

Neutronographische Bestimmung der Kristallstrukturparameter von Dy2O3, Tm2O3 und α -Mn2O3
journal, January 1963


X-ray structure determination of the rare earth oxides (Er 1− u Gd u ) 2 O 3 applying the Rietveld method
journal, September 2002

  • Heiba, Zein; Okuyucu, Hasan; Hascicek, Y. S.
  • Journal of Applied Crystallography, Vol. 35, Issue 5
  • DOI: 10.1107/S0021889802010555

X-ray structure and microstructure determination of the mixed sesquioxides (Eu 1− x Yb x ) 2 O 3 prepared by a sol–gel process
journal, November 2003


X-ray diffraction analysis of powder and thin film of (Gd1-xYx)2O3 prepared by sol-gel process
journal, March 2008


Structure and microstructure characterization of the mixed sesquioxides (Gd 1− x Yb x ) 2 O 3 and (Gd 1− x Ho x ) 2 O 3 prepared by sol–gel process
journal, March 2005

  • Heiba, Z. K.; Arda, L.; Hascicek, Y. S.
  • Journal of Applied Crystallography, Vol. 38, Issue 2
  • DOI: 10.1107/S0021889805000609

XRD, IR, and Raman investigations of structural properties of Dy2-xHox O3 prepared by sol gel procedure
journal, March 2012

  • Heiba, Z. K.; Bakr Mohamed, M.; Fuess, H.
  • Crystal Research and Technology, Vol. 47, Issue 5
  • DOI: 10.1002/crat.201200032

High-pressure Syntheses and Crystal Structures of Monoclinic B-Ho2O3 and Orthorhombic HoGaO3
journal, September 2009

  • Hering, Stefanie A.; Huppertz, Hubert
  • Zeitschrift für Naturforschung B, Vol. 64, Issue 9
  • DOI: 10.1515/znb-2009-0907

R�ntgenographische Untersuchung an Einkristallen von monoklinem Tb2O3
journal, December 1968

  • Hubbert-Paletta, E.; M�ller-Buschbau, Hk.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 363, Issue 3-4
  • DOI: 10.1002/zaac.19683630306

Electron density distribution and chemical bonding of Ln2O3 (Ln = Y, Tm, Yb) from powder X-ray diffraction data by the maximum-entropy method
journal, September 1994

  • Ishibashi, H.; Shimomoto, K.; Nakahigashi, K.
  • Journal of Physics and Chemistry of Solids, Vol. 55, Issue 9
  • DOI: 10.1016/0022-3697(94)90004-3

Effect of Annealing Environment on Low-Temperature Magnetic and Dielectric Properties of EuCo 0.5 Mn 0.5 O 3
journal, July 2014

  • Katari, Vasundhara; Achary, S. N.; Deshpande, S. K.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 31
  • DOI: 10.1021/jp501654c

The Structure of C-type Gd2O3. A Powder Neutron Diffraction Study using Enriched 160Gd
journal, January 2011

  • Kennedy, Brendan J.; Avdeev, Max
  • Australian Journal of Chemistry, Vol. 64, Issue 1
  • DOI: 10.1071/CH10310

The structure of B-type Sm2O3. A powder neutron diffraction study using enriched 154Sm
journal, September 2011


Neutron-diffraction study of the structure of the A-form of the rare earth sesquioxides
journal, September 1953


Paramagnetic and Nuclear Scattering Cross Sections of Holmium Sesquioxide
journal, April 1958

  • Koehler, W. C.; Wollan, E. O.; Wilkinson, M. K.
  • Physical Review, Vol. 110, Issue 1
  • DOI: 10.1103/PhysRev.110.37

Crystal structure of monoclinic samarium and cubic europium sesquioxides and bound coherent neutron scattering lengths of the isotopes 154Sm and 153Eu
journal, January 2016

  • Kohlmann, Holger; Hein, Christina; Kautenburger, Ralf
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 231, Issue 9
  • DOI: 10.1515/zkri-2016-1984

Structural and spectroscopic studies of Eu3+ doped Lu2O3–Gd2O3 solid solutions
journal, April 2014


Elaboration et proprietes magnetiques de monocristaux d'oxyde de praseodyme Pr2O3
journal, January 1976


A synchrotron X-ray study of the electron density in C-type rare earth oxides
journal, June 1996

  • Maslen, E. N.; Streltsov, V. A.; Ishizawa, N.
  • Acta Crystallographica Section B Structural Science, Vol. 52, Issue 3
  • DOI: 10.1107/S0108768195013371

Crystal data on C -type terbium sesquioxide (Tb 2 O 3 )
journal, October 1971


Magnetic properties of trivalent Sm ions in SmxY2−xO3
journal, October 2009


Magnetic Structures of Er 2 O 3 and Yb 2 O 3
journal, December 1968


Zur Struktur der A-Form der Sesquioxide der Seltenen Erden. II. Strukturuntersuchung an Nd2O3
journal, February 1966

  • M�ller-Buschbaum, H.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 343, Issue 1-2
  • DOI: 10.1002/zaac.19663430103

Zur Struktur der A-Form der Sesquioxide der Seltenen Erden. Strukturuntersuchungen an La2O3
journal, November 1965

  • M�ller-Buschbaum, Hk.; Schnering, H. G. V.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 340, Issue 5-6
  • DOI: 10.1002/zaac.19653400503

Rapid and Energy-Saving Microwave-Assisted Solid-State Synthesis of Pr 3+ -, Eu 3+ -, or Tb 3+ -Doped Lu 2 O 3 Persistent Luminescence Materials
journal, July 2016

  • Pedroso, Cássio C. S.; Carvalho, José M.; Rodrigues, Lucas C. V.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 30
  • DOI: 10.1021/acsami.6b04683

New X-ray powder diffraction data and Rietveld refinement for Gd 2 O 3 monodispersed fine spherical particles
journal, February 2003

  • Pires, Ana Maria; Davolos, Marian Rosaly; Paiva-Santos, Carlos O.
  • Journal of Solid State Chemistry, Vol. 171, Issue 1-2
  • DOI: 10.1016/S0022-4596(02)00224-4

The observation of face centred cubic Gd, Tb, Dy, Ho, Er and Tm in the form of thin films and their oxidation
journal, January 1973


Structural Change of C-Rare Earth Sesquioxides Yb2O3 and Er2O3 as a Function of Temperature [C型希土類酸化物Yb2O3及びEr2O3の高温構造変化]
journal, January 1985

  • Saiki, Atsushi; Ishizawa, Nobuo; Mizutani, Nobuyasu
  • Journal of the Ceramic Association, Japan, Vol. 93, Issue 1082
  • DOI: 10.2109/jcersj1950.93.1082_649

Probing Complex Disorder in Ce 1- x Gd x O 2- x /2 Using the Pair Distribution Function Analysis
journal, March 2012

  • Scavini, Marco; Coduri, Mauro; Allieta, Mattia
  • Chemistry of Materials, Vol. 24, Issue 7
  • DOI: 10.1021/cm203819u

Single crystals of rare earth oxides from reducing halide melts
journal, April 1989


Crystal Structure and Phase Transitions of Gd(CO 3 )OH Studied by Synchrotron Powder Diffraction
journal, August 2010

  • Sheu, Hwo-Shuenn; Shih, Wei-Ju; Chuang, Wei-Tsung
  • Journal of the Chinese Chemical Society, Vol. 57, Issue 4B
  • DOI: 10.1002/jccs.201000130

Precise determination of the lattice parameters of holmium and erbium sesquioxides at elevated temperatures
journal, June 1969


On the phase interval PrO1.50 to PrO1.71 in the praseodymium oxide-oxygen system
journal, May 1971

  • Turcotte, Rhéal P.; Warmkessel, Joyce M.; Tilley, Richard J. D.
  • Journal of Solid State Chemistry, Vol. 3, Issue 2
  • DOI: 10.1016/0022-4596(71)90039-9

Synthesis and characterization of spherical and rod like nanocrystalline Nd2O3 phosphors
journal, January 2011


Structural and oxide ion conductivity studies on Yb1−xBixO1.5 (0.00⩽x⩽0.50) composites
journal, May 2014


Core and shell structure of ytterbium sesquioxide nanoparticles
journal, July 2010

  • Vucinic-Vasic, Milica; Kremenovic, Aleksandar; Nikolic, Aleksandar S.
  • Journal of Alloys and Compounds, Vol. 502, Issue 1
  • DOI: 10.1016/j.jallcom.2010.03.158

Ytterbium L III -edge anomalous scattering measured with synchrotron radiation powder diffraction
journal, September 1987

  • Will, G.; Masciocchi, N.; Hart, M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 43, Issue 5
  • DOI: 10.1107/S010876738709874X

Eine Notiz zum A-Typ der Lanthanoidoxide: �ber Pr2O3
journal, October 1985

  • Wolf, H. C. R.; Hoppe, R.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 529, Issue 10
  • DOI: 10.1002/zaac.19855291009

Single Crystals of B-Type Er 2 O 3
journal, September 2008

  • Wontcheu, Joseph; Schleid, Thomas
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 634, Issue 11
  • DOI: 10.1002/zaac.200870165

A refinement of the crystal structure of monoclinic europium sesquioxide
journal, March 1979

  • Yakel, H. L.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 35, Issue 3
  • DOI: 10.1107/S0567740879004167

Structural phase transitions of cubic Gd 2 O 3 at high pressures
journal, August 2008


Er 3+ -Based Diureasil Organic−Inorganic Hybrids
journal, November 2008

  • Molina, C.; Ferreira, R. A. S.; Poirier, G.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 49
  • DOI: 10.1021/jp805777j

Synthesis, characterization and optical studies on lanthanide-doped CdS quantum dots: new insights on CdS → lanthanide energy transfer mechanisms
journal, January 2011

  • Planelles-Aragó, José; Cordoncillo, Eloisa; Ferreira, Rute A. S.
  • J. Mater. Chem., Vol. 21, Issue 4
  • DOI: 10.1039/C0JM03188G

Spectral study of the stimulated emission of Nd^3+ in fluorotellurite bulk glass
journal, January 2013