scholarly journals Thermodynamics of Molybdenum Trioxide Encapsulated in Zeolite Y

2021 ◽  
Author(s):  
Xianghui Zhang ◽  
Andrew Strzelecki ◽  
Cody Cockreham ◽  
Vitaliy Goncharov ◽  
Houqian Li ◽  
...  
Keyword(s):  
Molybdenum Trioxide ◽  
Zeolite Y ◽  
Formation Enthalpy ◽  
Solution Calorimetry ◽  
Metal Species ◽  
Enthalpies Of Formation ◽  
Host Interactions ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide

Zeolites with encapsulated transition metal species are extensively applied in the chemical industry as heterogenous catalysts for favorable kinetic pathways. To elucidate the energetic insights into formation of subnano-sized molybdenum trioxide (MoO) encapsulated/confined in zeolite Y (FAU) from constituent oxides, we performed a systematic experimental thermodynamic study using high temperature oxide melt solution calorimetry as the major tool. Specifically, the formation enthalpy of each MoO/FAU is less endothermic than corresponding zeolite Y, suggesting enhanced thermodynamic stability. As Si/Al ratio increases, the enthalpies of formation of MoO/FAU with identical loading (5 Mo-wt%) tend to be less endothermic, ranging from 61.1 ± 1.8 (Si/Al = 2.9) to 32.8 ± 1.4 kJ/mol TO (Si/Al = 45.6). Coupled with spectroscopic, structural and morphological characterizations, we revealed intricate energetics of MoO – zeolite Y guest – host interactions likely determined by the subtle redox and/or phase evolutions of encapsulated MoO.

scholarly journals Thermodynamics of Molybdenum Trioxide (MoO3) Encapsulated in Zeolite Y

2021 ◽  
Author(s):  
Xianghui Zhang ◽  
Andrew Strzelecki ◽  
Cody Cockreham ◽  
Vitaliy Goncharov ◽  
Houqian Li ◽  
...  
Keyword(s):  
Molybdenum Trioxide ◽  
Zeolite Y ◽  
Formation Enthalpy ◽  
Solution Calorimetry ◽  
Metal Species ◽  
Enthalpies Of Formation ◽  
Host Interactions ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide

Zeolites with encapsulated transition metal species are extensively applied in the chemical industry as heterogenous catalysts for favorable kinetic pathways. To elucidate the energetic insights into formation of subnano-sized molybdenum trioxide (MoO) encapsulated/confined in zeolite Y (FAU) from constituent oxides, we performed a systematic experimental thermodynamic study using high temperature oxide melt solution calorimetry as the major tool. Specifically, the formation enthalpy of each MoO/FAU is less endothermic than corresponding zeolite Y, suggesting enhanced thermodynamic stability. As Si/Al ratio increases, the enthalpies of formation of MoO/FAU with identical loading (5 Mo-wt%) tend to be less endothermic, ranging from 61.1 ± 1.8 (Si/Al = 2.9) to 32.8 ± 1.4 kJ/mol TO (Si/Al = 45.6). Coupled with spectroscopic, structural and morphological characterizations, we revealed intricate energetics of MoO – zeolite Y guest – host interactions likely determined by the subtle redox and/or phase evolutions of encapsulated MoO.

scholarly journals Thermodynamics of Molybdenum Trioxide (MoO3) Encapsulated in Zeolite Y

2021 ◽  
Author(s):  
Xianghui Zhang ◽  
Vitaliy Goncharov ◽  
Cody Cockreham ◽  
Houqian Li ◽  
Junming Sun ◽  
...  
Keyword(s):  
Molybdenum Trioxide ◽  
Zeolite Y ◽  
Formation Enthalpy ◽  
Solution Calorimetry ◽  
Catalytic Performance ◽  
Metal Species ◽  
Enthalpies Of Formation ◽  
Host Interactions ◽  
Oxide Melt ◽  
High Temperature Oxide

Zeolites with encapsulated transition metal species are extensively applied in the chemical industry as heterogenous catalysts for favorable kinetic pathways. To elucidate the energetic insights into formation of subnano-sized molybdenum trioxide (MoO3) encapsulated/confined in zeolite Y (FAU) from constituent oxides, we performed a systematic experimental thermodynamic study using high temperature oxide melt solution calorimetry as the major tool. Specifically, the formation enthalpy of each MoO3/FAU is less endothermic than corresponding zeolite Y, suggesting enhanced thermodynamic stability. As Si/Al ratio increases, the enthalpies of formation of MoO3/FAU with identical MoO3 loading tends to be less endothermic, ranging from 61.1 ± 1.8 (Si/Al = 2.9) to 32.8 ± 1.4 kJ/mol TO2 (Si/Al = 45.6). Coupled with spectroscopic, structural and morphological characterizations, and catalytic performance tests, we revealed intricate energetics of MoO3 – zeolite Y guest – host interactions and catalytic performance governed by the phase evolutions of encapsulated MoO3.

Thermochemistry of Hf-Zirconolite, CaHf Ti2O7

1999 ◽  
Vol 556 ◽  
Author(s):  
Robert L. Putnam ◽  
Alexandra Navrotsky ◽  
Brian F. Woodfield ◽  
Jennifer L. Shapiro ◽  
Rebecca Stevens ◽  
...  
Keyword(s):  
Heat Capacity ◽  
High Temperature ◽  
Low Temperature ◽  
Adiabatic Calorimetry ◽  
Formation Enthalpy ◽  
Solution Calorimetry ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide ◽  
Capacity Data

AbstractThe formation enthalpy, - 3752.3 ± 4.7 kJ·mol−1, of Hf-zirconolite, CaHfTi2O7, was obtained using high temperature oxide-melt solution calorimetry. Combined with heat capacity data obtained using low temperature adiabatic calorimetry we report the heat capacity (Cp) and the standard molar formation energetics (ΔH°f. elements, Δ S°T, and ΔG°f. elements)for Hf-zirconolite from T = 298.15 K to T = 1500 K. Comparison of Hf-zirconolite with Zr-zirconolite is made.

Formation Enthalpies of Tetravalent Lanthanide Perovskites by High Temperature Oxide Melt Solution Calorimetry

2002 ◽  
Vol 718 ◽  
Author(s):  
S. V. Ushakov ◽  
J. Cheng ◽  
A. Navrotsky ◽  
J. R. Wu ◽  
S. M. Haile
Keyword(s):  
High Temperature ◽  
Rietveld Method ◽  
Thermal Analyses ◽  
Formation Enthalpy ◽  
Solution Calorimetry ◽  
Cell Parameters ◽  
Oxide Melt ◽  
Formation Enthalpies ◽  
High Temperature Oxide ◽  
Temperature Oxide

AbstractHigh-temperature oxide melt solution calorimetry was used to measure formation enthalpies for several compositions of perovskites of nominal stoichiometry BaPrO3 and BaCeO3. Samples were synthesized from chemical solution methods followed by calcination at 1100-1300°C. PrO2 was synthesized by oxidation of Pr6O11 in an oxygen flow at 280°C. The samples were characterized by microprobe, thermogravimetric and differential thermal analyses. Cell parameters were refined by the Rietveld method. Barium excess in the samples with respect to ideal stoichiometry was detected. Drop solution enthalpies were measured in a Calvet type twin microcalorimeter, using 3Na2O·4MoO3 solvent at 702°C. Preliminary values of the formation enthalpy of BaPrO3 and BaCeO3 from oxides were -70 ±10 kJ/mol and -51 ±10 kJ/mol, respectively. They fall on the normal trend of energetics versus Goldschmidt tolerance factor and do not show any special stabilization of BaPrO3 relative to other MLnO3 perovskites.

Thermochemistry of Rare Earth Perovskites

MRS Advances ◽  
2016 ◽  
Vol 1 (38) ◽  
pp. 2695-2700 ◽  
Author(s):  
Dawei Feng ◽  
Alexandra Navrotsky
Keyword(s):  
Rare Earth ◽  
Solid Solutions ◽  
Solution Calorimetry ◽  
Sodium Content ◽  
Enthalpies Of Formation ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide ◽  
Image Position ◽  
Light Rare Earth Elements

AbstractThe rare earth (RE) mineral loparite with the chemical composition (RE, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light rare earth elements (LREE) as well as niobium and tantalum. The enthalpies of formation of RE0.67-xNa3xTiO3 (RE = La, Ce) and Ca1-2xNaxLaxTiO3 from oxides and elements of lanthanum and cerium perovskites and their solid solutions have been obtained using high temperature oxide melt solution calorimetry. RE0.67-xNa3xTiO3 (RE = La, Ce) perovskites become more stable relative to oxide components as sodium content increases. Na0.5Ce0.5TiO3 and Na0.5La0.5TiO3 can be considered stable endmembers in natural loparite minerals. For perovskite solid solutions Ca1-2xNaxLaxTiO3, the enthalpies of formation from the constituent oxides $\Delta {\rm{H}}_{{\rm{f}},\,{\rm{ox}}}^^\circ$ become more exothermic with increasing Na+La content, suggesting a stabilizing effect of the substitution 2Ca2+ → Na+ + La3+ on the perovskite structure. The trend of increasing thermodynamic stability with decreasing structural distortion is similar to that seen in many other ABO3 perovskites.

Enthalpies of formation of LaBO3perovskites (B = Al, Ga, Sc, and In)

2003 ◽  
Vol 18 (10) ◽  
pp. 2501-2508 ◽  
Author(s):  
Jihong Cheng ◽  
Alexandra Navrotsky
Keyword(s):  
High Temperature ◽  
Enthalpy Of Formation ◽  
Solution Calorimetry ◽  
Tolerance Factor ◽  
Enthalpies Of Formation ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide ◽  
First Time ◽  
The Enthalpy Of Formation

Enthalpies of formation from constituent oxides and elements at 298 K were determined by high-temperature oxide melt solution calorimetry for a group of technologically important perovskites LaBO3(B = La, Ga, Sc, and In). Enthalpies of formation from oxides of LaAlO3and LaGaO3are −69.61 ± 3.23 kJ/mol and −52.39 ± 1.99 kJ/mol, respectively. The data were consistent with literature values obtained using other methods. The enthalpies of formation of LaScO3and LaInO3from oxides were reported for the first time as −38.64 ± 2.30 kJ/mol and −23.99 ± 2.31 kJ/mol, respectively. As seen for other perovskites, as the tolerance factor deviates more from unity (in the order Al, Ga, Sc, In), the enthalpy of formation from oxides becomes less exothermic, indicating a less stable structure with respect to the constituent oxides.

scholarly journals Enthalpies of formation of lanthanide oxyapatite phases

2001 ◽  
Vol 16 (10) ◽  
pp. 2780-2783 ◽  
Author(s):  
A. S. Risbud ◽  
K. B. Helean ◽  
M. C. Wilding ◽  
P. Lu ◽  
A. Navrotsky
Keyword(s):  
Structural Formula ◽  
Solution Calorimetry ◽  
Enthalpies Of Formation ◽  
Enthalpies Of Solution ◽  
Thermodynamic Cycles ◽  
Oxide Melt ◽  
Formation Enthalpies ◽  
High Temperature Oxide ◽  
Standard Enthalpies Of Formation ◽  
Temperature Oxide

A family of lanthanide silicates adopts an oxyapatitelike structure with structural formula Ln9.33 0.67(SiO4)6O2 (Ln = La, Sm, Nd, Gd,   = vacancy). The enthalpies of solution, ΔHS, for these materials and their corresponding binary oxides were determined by high-temperature oxide melt solution calorimetry using molten 2PbO B2O3 at 1078 K. These data were used to complete thermodynamic cycles to calculate enthalpies of formation from the oxides, ΔH0 f-oxides (kJ/mol): La9.33 0.67(SiO4)6O2 = 776.3 ± 17.9, Nd9.33 0.67(SiO4)6O2 = 760.4 ± 31.9, Sm9.33 0.67(SiO4)6O2 = 590.3 ± 18.6, and Gd9.33 0.67(SiO4)6O2 = 446.9 ± 21.9. Reference data were used to calculate the standard enthalpies of formation from the elements, ΔH0 f (kJ/mol): La9.33 0.67(SiO4)6O2 = 14611.0 ± 19.4, Nd9.33 0.67(SiO4)6O2 = 14661.5 ± 32.2, Sm9.33 0.67(SiO4)6O2 = -14561.7 ±; 20.8, and Gd9.33 0.67(SiO4)6O2 = -14402.7 ± 28.2. The formation enthalpies become more endothermic as the ionic radius of the lanthanide ion decreases.

Enthalpies of Formation of LaMO3 Perovskites (M = Cr, Fe, Co, and Ni)

2005 ◽  
Vol 20 (1) ◽  
pp. 191-200 ◽  
Author(s):  
Jihong Cheng ◽  
Alexandra Navrotsky ◽  
Xiao-Dong Zhou ◽  
Harlan U. Anderson
Keyword(s):  
High Temperature ◽  
Relative Stability ◽  
Solution Calorimetry ◽  
Enthalpies Of Formation ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide

Enthalpies of formation from constituent oxides and elements at 298 K were determined by high-temperature oxide melt solution calorimetry for a group of technologically important perovskites LaMO3 (M = Cr, Fe, Co, and Ni). The enthalpies of formation of LaCrO3 and LaFeO3 from oxides (La2O3 and Cr2O3 or Fe2O3) are –70.06 ± 2.79 kJ/mol and –64.58 ± 2.32 kJ/mol, respectively. The enthalpies of formation of LaCoO3 and LaNiO3 from oxides (La2O3 and CoO or NiO) and O2 are −107.64 ± 1.77 kJ/mol and –57.31 ± 2.55 kJ/mol, respectively. All these data are evaluated and found to be consistent with literature values obtained using other methods. The relative stability among these four perovskites decreases in the order of Cr, Fe, Co, Ni.

scholarly journals Development of high-temperature oxide melt solution calorimetry for p-block element containing materials – CORRIGENDUM

2020 ◽  
pp. 1-1
Author(s):  
Mykola Abramchuk ◽  
Kristina Lilova ◽  
Tamilarasan Subramani ◽  
Ray Yoo ◽  
Alexandra Navrostky
Keyword(s):  
High Temperature ◽  
Solution Calorimetry ◽  
Block Element ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide

Thermochemistry of lanthanum zirconate pyrochlore

2009 ◽  
Vol 24 (11) ◽  
pp. 3350-3357 ◽  
Author(s):  
A.V. Radha ◽  
Sergey V. Ushakov ◽  
Alexandra Navrotsky
Keyword(s):  
Melting Point ◽  
Enthalpy Of Formation ◽  
Sodium Molybdate ◽  
Solution Calorimetry ◽  
Standard Enthalpy Of Formation ◽  
Lanthanum Zirconate ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide ◽  
The Enthalpy Of Formation

A thermodynamic study was carried out to resolve discrepancies in the enthalpy of formation and related parameters for lanthanum zirconate pyrochlore. The homogeneity field for single phase pyrochlore formation was determined to be ∼33–35 mol% La2O3 at 1500 °C. High-temperature oxide melt drop solution calorimetry was performed in sodium molybdate and lead borate solvents on three compositions ranging from La1.98Zr2.01O7 to La2.07Zr1.95O7. The enthalpy of formation from oxides at 25 °C, ΔH0f,ox, for stoichiometric lanthanum zirconate pyrochlore is −107.3 ± 5.1 kJ/mol, and the standard enthalpy of formation from elements, ΔH0f,el, is −4102.2 ± 6.0 kJ/mol. La2Zr2O7 pyrochlore was found by differential thermal analysis to be stable up to its melting point. The melting point and the fusion enthalpy of La2Zr2O7 pyrochlore were measured as 2295 ± 10 °C and ∼350 kJ/mol, respectively.

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