Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals

Research output: Contribution to journalArticleResearchpeer review

Authors

  • Andreas Schaate
  • Pascal Roy
  • Adelheid Godt
  • Jann Lippke
  • Florian Waltz
  • Michael Wiebcke
  • Peter Behrens

External Research Organisations

  • Bielefeld University
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Details

Original languageEnglish
Pages (from-to)6643-6651
Number of pages9
JournalChemistry - a European journal
Volume17
Issue number24
Publication statusPublished - 5 May 2011

Abstract

We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH2 (UiO- 66-NH2), Zr-bpdc (UiO-67), and Zr- tpdc-NH2 (UiO-68-NH2) (H2bdc: terephthalic acid, H2bpdc: biphenyl-4,4'- dicarboxylic acid, H2tpdc: terphenyl- 4,4"-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH2. Zr- tpdc-NH2, a material with a structure analogous to that of Zr-bdc and Zr- bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1"-terphenyl- 4,4"-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.

Keywords

    metal-organic frameworks, microporous materials, modulation approach, nanoparticles, zirconium

ASJC Scopus subject areas

Cite this

Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals. / Schaate, Andreas; Roy, Pascal; Godt, Adelheid et al.
In: Chemistry - a European journal, Vol. 17, No. 24, 05.05.2011, p. 6643-6651.

Research output: Contribution to journalArticleResearchpeer review

Schaate, A, Roy, P, Godt, A, Lippke, J, Waltz, F, Wiebcke, M & Behrens, P 2011, 'Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals', Chemistry - a European journal, vol. 17, no. 24, pp. 6643-6651. https://doi.org/10.1002/chem.201003211
Schaate, A., Roy, P., Godt, A., Lippke, J., Waltz, F., Wiebcke, M., & Behrens, P. (2011). Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals. Chemistry - a European journal, 17(24), 6643-6651. https://doi.org/10.1002/chem.201003211
Schaate A, Roy P, Godt A, Lippke J, Waltz F, Wiebcke M et al. Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals. Chemistry - a European journal. 2011 May 5;17(24):6643-6651. doi: 10.1002/chem.201003211
Schaate, Andreas ; Roy, Pascal ; Godt, Adelheid et al. / Modulated synthesis of Zr-based metal-organic frameworks : From nano to single crystals. In: Chemistry - a European journal. 2011 ; Vol. 17, No. 24. pp. 6643-6651.
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abstract = "We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH2 (UiO- 66-NH2), Zr-bpdc (UiO-67), and Zr- tpdc-NH2 (UiO-68-NH2) (H2bdc: terephthalic acid, H2bpdc: biphenyl-4,4'- dicarboxylic acid, H2tpdc: terphenyl- 4,4{"}-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH2. Zr- tpdc-NH2, a material with a structure analogous to that of Zr-bdc and Zr- bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1{"}-terphenyl- 4,4{"}-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.",
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T1 - Modulated synthesis of Zr-based metal-organic frameworks

T2 - From nano to single crystals

AU - Schaate, Andreas

AU - Roy, Pascal

AU - Godt, Adelheid

AU - Lippke, Jann

AU - Waltz, Florian

AU - Wiebcke, Michael

AU - Behrens, Peter

PY - 2011/5/5

Y1 - 2011/5/5

N2 - We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH2 (UiO- 66-NH2), Zr-bpdc (UiO-67), and Zr- tpdc-NH2 (UiO-68-NH2) (H2bdc: terephthalic acid, H2bpdc: biphenyl-4,4'- dicarboxylic acid, H2tpdc: terphenyl- 4,4"-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH2. Zr- tpdc-NH2, a material with a structure analogous to that of Zr-bdc and Zr- bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1"-terphenyl- 4,4"-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.

AB - We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH2 (UiO- 66-NH2), Zr-bpdc (UiO-67), and Zr- tpdc-NH2 (UiO-68-NH2) (H2bdc: terephthalic acid, H2bpdc: biphenyl-4,4'- dicarboxylic acid, H2tpdc: terphenyl- 4,4"-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH2. Zr- tpdc-NH2, a material with a structure analogous to that of Zr-bdc and Zr- bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1"-terphenyl- 4,4"-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.

KW - metal-organic frameworks

KW - microporous materials

KW - modulation approach

KW - nanoparticles

KW - zirconium

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DO - 10.1002/chem.201003211

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VL - 17

SP - 6643

EP - 6651

JO - Chemistry - a European journal

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