The Role of PentaCoordinated Al3+ Ions in the High Temperature Phase Transformation of γ-Al2O3

Journal Article · Thu Jun 26 04:00:00 EDT 2008 · Journal of Physical Chemistry C, 112(25):9486–9492

DOI:https://doi.org/10.1021/jp802631u· OSTI ID:935060

Kwak, Ja Hun; Hu, Jian Zhi; Lukaski, Adrienne C; Kim, Do Heui; Szanyi, Janos; Peden, Charles HF

In this work, the structural stability of gamma-alumina (γ-Al2O3) was investigated by a combination of XRD and high resolution solid state 27Al MAS NMR at an ultra-high magnetic field of 21.1 tesla. XRD measurements show that γ-Al2O3 undergoes a phase transition to θ-Al2O3 during calcination at 1000oC for 10hr. The formation of the θ-Al2O3 phase is further confirmed by 27Al MAS NMR; additional 27Al peaks centered at 10.5 and ~78 ppm were observed in samples calcined at this high temperature. Both the XRD and NMR results indicate that, after calcination at 1000°C for 10 hrs, the ratio of the θ-Al2O3 phase to the total alumina in samples modified by either BaO or La2O3 is significantly reduced in comparison with γ-Al2O3. 27Al MAS NMR spectra revealed that the reduction in the extent of θ-Al2O3 formation was highly correlated with the reduction in the amount of penta-coordinated aluminum ions, measured after 500°C calcination, in both BaO- and La2O3-modified γ-Al2O3 samples. These results strongly suggest that the penta-coordinated aluminum ions, present exclusively on the surface of γ-Al2O3, play a critical role in the phase transformation of γ-Al2O3 to θ-Al2O3. The role of the modifiers, in our case BaO or La2O3, is to convert the penta-coordinated aluminum ions into octahedral ones, thereby improving the thermal stabilities of the samples. Oxide additives, on the other hand, had no beneficial effect on preventing the specific surface area reduction that occurred during high temperature (≤1000°C) calcination.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 935060
• Report Number(s): PNNL-SA-58543; 9103a; KC0302010
• Journal Information: Journal of Physical Chemistry C, 112(25):9486–9492, Journal Name: Journal of Physical Chemistry C, 112(25):9486–9492 Journal Issue: 25 Vol. 112
• Country of Publication: United States
• Language: English

Related Subjects

27Al MAS NMR
36 MATERIALS SCIENCE
ALUMINIUM OXIDES
BARIUM OXIDES
BaO
CALCINATION
DOPED MATERIALS
Environmental Molecular Sciences Laboratory
LANTHANUM OXIDES
La2O3
PHASE TRANSFORMATIONS
STABILITY
SURFACE AREA
XRD
high magnetic field
penta-coordinated Al3+ ions
thermal stability
γ-Al2O3