Small-angle X-ray scattering documents the growth of metal-organic frameworks

Maarten Goesten; Eli Stavitski; Jana Juan-Alcañiz; Alberto Martiñez-Joaristi; Andrei V. Petukhov; Freek Kapteijn; Jorge Gascon

doi:10.1016/j.cattod.2012.08.044

Small-angle X-ray scattering documents the growth of metal-organic frameworks

Maarten Goesten^*, Eli Stavitski, Jana Juan-Alcañiz, Alberto Martiñez-Joaristi, Andrei V. Petukhov, Freek Kapteijn, Jorge Gascon

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

57 Scopus citations

Abstract

We present a combined in situ small- and wide-angle scattering (SAXS/WAXS) study on the crystallization of two topical metal-organic frameworks synthesized from similar metal and organic precursors: NH₂-MIL-53(Al) and NH₂-MIL-101(Al). A thorough analysis of SAXS data reveals the most important phenomena occurring during crystallization and unravels the effect of the solvent. NH₂-MIL-53(Al) growth follows two routes: (i) through direct hydrolysis of AlCl₃·6H₂O in water, and (ii) via the intermediate NH₂-MOF-235(Al), which forms in pure DMF or DMF/H₂O mixtures. In the case of pure H₂O as solvent, formation of NH₂-MIL-53(Al) crystals proceeds through steady growth in all three dimensions. The addition of DMF to the synthesis mixture results in amorphous scattering entities forming very rapidly and subsequently arranging into the intermediate phase, NH₂-MOF-235(Al). In DMF/H₂O mixtures, amorphous precursors develop in rapid fashion with fractal character dominating, followed by densification, crystallization of NH₂-MOF- 235(Al) and slow transformation into NH₂-MIL-53(Al). Formation of NH₂-MIL-101(Al) only occurs when pure DMF is used as solvent, and it always proceeds through the formation of the intermediate NH₂-MOF- 235(Al). In this case a smooth scatterer surface is observed, with morphology and size constant in time.

Original language	English (US)
Pages (from-to)	120-127
Number of pages	8
Journal	Catalysis Today
Volume	205
DOIs	https://doi.org/10.1016/j.cattod.2012.08.044
State	Published - Apr 30 2013
Externally published	Yes

Keywords

Crystallization
In situ
Metal organic framework
SAXS/WAXS

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1016/j.cattod.2012.08.044

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title = "Small-angle X-ray scattering documents the growth of metal-organic frameworks",

abstract = "We present a combined in situ small- and wide-angle scattering (SAXS/WAXS) study on the crystallization of two topical metal-organic frameworks synthesized from similar metal and organic precursors: NH2-MIL-53(Al) and NH2-MIL-101(Al). A thorough analysis of SAXS data reveals the most important phenomena occurring during crystallization and unravels the effect of the solvent. NH2-MIL-53(Al) growth follows two routes: (i) through direct hydrolysis of AlCl3·6H2O in water, and (ii) via the intermediate NH2-MOF-235(Al), which forms in pure DMF or DMF/H2O mixtures. In the case of pure H2O as solvent, formation of NH2-MIL-53(Al) crystals proceeds through steady growth in all three dimensions. The addition of DMF to the synthesis mixture results in amorphous scattering entities forming very rapidly and subsequently arranging into the intermediate phase, NH2-MOF-235(Al). In DMF/H2O mixtures, amorphous precursors develop in rapid fashion with fractal character dominating, followed by densification, crystallization of NH2-MOF- 235(Al) and slow transformation into NH2-MIL-53(Al). Formation of NH2-MIL-101(Al) only occurs when pure DMF is used as solvent, and it always proceeds through the formation of the intermediate NH2-MOF- 235(Al). In this case a smooth scatterer surface is observed, with morphology and size constant in time.",

keywords = "Crystallization, In situ, Metal organic framework, SAXS/WAXS",

author = "Maarten Goesten and Eli Stavitski and Jana Juan-Alca{\~n}iz and Alberto Marti{\~n}ez-Joaristi and Petukhov, {Andrei V.} and Freek Kapteijn and Jorge Gascon",

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T1 - Small-angle X-ray scattering documents the growth of metal-organic frameworks

AU - Goesten, Maarten

AU - Stavitski, Eli

AU - Juan-Alcañiz, Jana

AU - Martiñez-Joaristi, Alberto

AU - Petukhov, Andrei V.

AU - Kapteijn, Freek

AU - Gascon, Jorge

PY - 2013/4/30

Y1 - 2013/4/30

N2 - We present a combined in situ small- and wide-angle scattering (SAXS/WAXS) study on the crystallization of two topical metal-organic frameworks synthesized from similar metal and organic precursors: NH2-MIL-53(Al) and NH2-MIL-101(Al). A thorough analysis of SAXS data reveals the most important phenomena occurring during crystallization and unravels the effect of the solvent. NH2-MIL-53(Al) growth follows two routes: (i) through direct hydrolysis of AlCl3·6H2O in water, and (ii) via the intermediate NH2-MOF-235(Al), which forms in pure DMF or DMF/H2O mixtures. In the case of pure H2O as solvent, formation of NH2-MIL-53(Al) crystals proceeds through steady growth in all three dimensions. The addition of DMF to the synthesis mixture results in amorphous scattering entities forming very rapidly and subsequently arranging into the intermediate phase, NH2-MOF-235(Al). In DMF/H2O mixtures, amorphous precursors develop in rapid fashion with fractal character dominating, followed by densification, crystallization of NH2-MOF- 235(Al) and slow transformation into NH2-MIL-53(Al). Formation of NH2-MIL-101(Al) only occurs when pure DMF is used as solvent, and it always proceeds through the formation of the intermediate NH2-MOF- 235(Al). In this case a smooth scatterer surface is observed, with morphology and size constant in time.

AB - We present a combined in situ small- and wide-angle scattering (SAXS/WAXS) study on the crystallization of two topical metal-organic frameworks synthesized from similar metal and organic precursors: NH2-MIL-53(Al) and NH2-MIL-101(Al). A thorough analysis of SAXS data reveals the most important phenomena occurring during crystallization and unravels the effect of the solvent. NH2-MIL-53(Al) growth follows two routes: (i) through direct hydrolysis of AlCl3·6H2O in water, and (ii) via the intermediate NH2-MOF-235(Al), which forms in pure DMF or DMF/H2O mixtures. In the case of pure H2O as solvent, formation of NH2-MIL-53(Al) crystals proceeds through steady growth in all three dimensions. The addition of DMF to the synthesis mixture results in amorphous scattering entities forming very rapidly and subsequently arranging into the intermediate phase, NH2-MOF-235(Al). In DMF/H2O mixtures, amorphous precursors develop in rapid fashion with fractal character dominating, followed by densification, crystallization of NH2-MOF- 235(Al) and slow transformation into NH2-MIL-53(Al). Formation of NH2-MIL-101(Al) only occurs when pure DMF is used as solvent, and it always proceeds through the formation of the intermediate NH2-MOF- 235(Al). In this case a smooth scatterer surface is observed, with morphology and size constant in time.

KW - Crystallization

KW - In situ

KW - Metal organic framework

KW - SAXS/WAXS

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DO - 10.1016/j.cattod.2012.08.044

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AN - SCOPUS:84875211316

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VL - 205

SP - 120

EP - 127

JO - Catalysis Today

JF - Catalysis Today

ER -

Small-angle X-ray scattering documents the growth of metal-organic frameworks

Abstract

Keywords

ASJC Scopus subject areas

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