Samarium doped ceria (SDC) synthesized by a metal triethanolamine complex decomposition method: Characterization and an ionic conductivity study

Wattanathana, Worawat; Veranitisagul, Chatchai; Wannapaiboon, Suttipong; Klysubun, Wantana; Koonsaeng, Nattamon; Laobuthee, Apirat

doi:10.1016/j.ceramint.2017.04.162

Cited by 33 publications

(19 citation statements)

References 40 publications

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“…38,69 The activation energies for oxygen vacancy motion in Smand Eu-substituted CeO2 determined here are the same within error; this supports the prevalent assumption that the activation energy for vacancy hops is largely independent of the substituent. 25 The activation energy for oxygen diffusion in 15 at% Sm-substituted CeO2 has previously been reported as 1.00 eV from the DC conductivity 34 and 0.84 eV from impedance spectroscopy 35 . An activation energy for oxygen diffusion in 15 at% Eu-substituted CeO2 has not been reported to our knowledge, but impedance spectroscopy experiments have yielded activation energies for 10 at% and 20 at% Eusubstituted CeO2 of 0.64 eV and 0.89 eV, respectively.…”

Section: Sm-and Eu-substituted Ceo2mentioning

confidence: 97%

“…The exemplar phase of this class of conductors is Gd-doped ceria (GDC), 29 which remains a common electrolyte (and anode component) used in solid oxide fuel cells. 30,31 While the conductivity mechanism and activation energy barriers in GDC and other Ln-substituted CeO2 phases have typically been probed through impedance spectroscopy, DC conductivity, and oxygen permeability methods, [32][33][34][35][36][37] variable-temperature solid-state NMR studies have also provided complementary and atomic-level insights. Fuda et al first showed that 17 O spin-lattice relaxation (T1) measurements (up to 1000 °C) of CeO2 and Y-substituted CeO2 sensitively probed oxide-ion motion with a component at the Larmor frequency; Adler et al later reinterpreted the multiple T1 minima as evidence of two distinct time scales for motion corresponding to nearby oxygen vacancy hops and exchange of the observed oxygen itself with vacancies.…”

Section: Introductionmentioning

confidence: 99%

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A 17O paramagnetic NMR study of Sm2O3, Eu2O3, and Sm/Eu-substituted CeO2

Hope

Halat

Lee

et al. 2019

Solid State Nuclear Magnetic Resonance

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Paramagnetic solid-state NMR of lanthanide (Ln) containing materials can be challenging due to the high electron spin states possible for the Ln f electrons, which result in large paramagnetic shifts, and these difficulties are compounded for 17 O due to the low natural abundance and quadrupolar character. In this work, we present examples of 17 O NMR experiments for lanthanide oxides and strategies to overcome these difficulties. In particular, we record and assign the 17 O NMR spectra of monoclinic Sm2O3 and Eu2O3 for the first time, as well as performing density functional theory (DFT) calculations to gain further insight into the spectra. The temperature dependence of the Sm 3+ and Eu 3+ magnetic susceptibilities are investigated by measuring the 17 O shift of the cubic sesquioxides over a wide temperature range, which reveal non-Curie temperature dependence due to the presence of low-lying electronic states. This behaviour is reproduced by calculating the electron spin as a function of temperature, yielding shifts which agree well with the experimental values. Using the understanding of the magnetic behaviour gained from the sesquioxides, we then explore the local oxygen environments in 15 at% Sm-and Eu-substituted CeO2, with the 17 O NMR spectrum exhibiting signals due to environments with zero, one and two nearest neighbour Ln ions, as well as further splitting due to oxygen vacancies. Finally, we extract an activation energy for oxygen vacancy motion in these systems of 0.35 ± 0.02 eV from the Arrhenius temperature dependence of the 17 O T1 relaxation constants, which is found to be independent of the Ln ion within error. The relation of this activation energy to literature values for oxygen diffusion in Ln-substituted CeO2 is discussed to infer mechanistic information which can be applied to further develop these materials as solid-state oxide-ion conductors. Recent efforts by Heinzmann et al. have shown that 17 O NMR (and T1) measurements can be applied to GDC to quantify doping behaviour and to extract activation energy values that can be ascribed to oxideion motion. 41 However, to our knowledge 17 O NMR and/or relaxometry-based techniques have not been used to study conduction in other Ln-substituted CeO2 materials, likely due to the aforementioned difficulties in interpreting NMR spectra of paramagnetic phases. In this work, we apply the lessons learned regarding the magnetic behaviour of Sm 3+ and Eu 3+ as seen in the paramagnetic 17 O NMR of the monoclinic Ln2O3 polymorphs to guide the analysis of variable-temperature 17 O spectra of Sm-and Eu-substituted CeO2.

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Section: Sm-and Eu-substituted Ceo2mentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

A 17O paramagnetic NMR study of Sm2O3, Eu2O3, and Sm/Eu-substituted CeO2

Hope

Halat

Lee

et al. 2019

Solid State Nuclear Magnetic Resonance

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“…In general, the electrical conductivity of NIMs follows the Vogel−Tammann−Fulcher (VTF) equation given as [ 38 ]

where σ is the conductivity, T is the absolute temperature, and A , B and T 0 are the constants reflecting the relationship between the conductivity and temperature. By combining with the Arrhenius expression, this equation can be rewritten as [ 39 , 40 ]

where E a is the activation energy and R is the Boltzmann constant. Figure 11 shows the logarithmic plot of σ versus 1000/ T derived from the conductive measurement for CaCO 3 -based NIMs at different ambient temperatures, and the activation energy can be determined as 2.261 × 10 3 eV according to equation (3.2).…”

Section: Resultsmentioning

confidence: 99%

In situ formation of surface-functionalized ionic calcium carbonate nanoparticles with liquid-like behaviours and their electrical properties

et al. 2018

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This paper reports a new route to synthesize calcium carbonate (CaCO3)-based nanoscale ionic materials (NIMs) via an in situ formation method to form the CaCO3 nanoparticles with a polysiloxane quaternary ammonium salt (PQAC) corona (PQAC-CaCO3 nanoparticles), followed by an ionic exchange reaction to fabricate a poly(ethylene glycol)-tailed sulfonate anion (NPEP) canopy. The chemical compositions and structures of the CaCO3-based NIMs synthesized in this work were confirmed by Fourier-transform infrared spectroscopy and solid-state 13C NMR spectroscopy. Transmission electron microscopic observation indicated that the CaCO3-based NIMs presented a rhombohedral shape with a well-defined core-shell structure, and they also obtained an NPEP canopy with a thickness of 4–6 nm. X-ray powder diffraction investigation confirmed that the CaCO3 inner core had a calcite crystalline structure, whereas the NPEP canopy was amorphous. The NPEP canopy was found to show a characteristic crystallization–melting behaviour in the presence of the ion bonding with PQAC-CaCO3 nanoparticles according to the characterization of differential scanning calorimetry. Thermogravimetric analysis indicated that the CaCO3-based NIMs achieved a high content of NPEP canopy as well as an improvement in thermal stability owing to the ion-bonding effect. Most of all, the CaCO3-based NIMs demonstrated a liquid-like behaviour above the critical temperature in the absence of solvent. Moreover, the CaCO3-based NIMs also showed a relatively high electrical conductivity with a temperature dependency due to the ionic conductive effect. This work will provide a more feasible and energy-saving methodology for the preparation of CaCO3-based NIMs to promote their industrialization and extensive applications.

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“…Among the available CeO2 synthesis routes, combustion synthesis is commonly used because it is straightforward and low-cost [2,[11][12][13][14][15]. Taking advantage of the heat released during precursor decomposition, product formation is achieved at low processing temperature in a very short time lapse.…”

Section: Introductionmentioning

confidence: 99%

Thermal decomposition of cerium triethanolamine complexes

et al. 2020

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Thermal decomposition of cerium triethanolamine complexes to cerium oxide, CeO2, in inert and oxidative atmospheres has been investigated by thermogravimetry combined with infrared evolved gas analysis; the main volatiles formed during thermal decomposition have been identified. Intermediates and final products have been characterized by infrared spectroscopy, X-Ray diffraction and elemental analysis. Several overlapping steps occurring along decomposition path have been identified and plausible reaction pathways are presented. It will be shown that decomposition starts around 200ºC independently of the atmosphere, but the endset temperature depends on the gas composition: the more inert the atmosphere the higher the endset temperature. Finally, the effect of the temperature and amount of triethanolamine used during compound synthesis is discussed.

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Samarium doped ceria (SDC) synthesized by a metal triethanolamine complex decomposition method: Characterization and an ionic conductivity study

Cited by 33 publications

References 40 publications

A 17O paramagnetic NMR study of Sm2O3, Eu2O3, and Sm/Eu-substituted CeO2

A 17O paramagnetic NMR study of Sm2O3, Eu2O3, and Sm/Eu-substituted CeO2

In situ formation of surface-functionalized ionic calcium carbonate nanoparticles with liquid-like behaviours and their electrical properties

Thermal decomposition of cerium triethanolamine complexes

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