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Highly mesoporous metal-organic framework assembled in a switchable solvent.

Peng L, Zhang J, Xue Z, Han B, Sang X, Liu C, Yang G - Nat Commun (2014)

Bottom Line: The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy.Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction.The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

View Article: PubMed Central - PubMed

Affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

ABSTRACT
The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

No MeSH data available.


Related in: MedlinePlus

Photographs of MOF synthesis in CO2-expanded DMF.(a) In pure DMF; (b) 2.0; (c) 4.5; (d) 6.6 MPa. (e) Phase separation in reaction system at 6.6 MPa after reaction for 3 h.
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f1: Photographs of MOF synthesis in CO2-expanded DMF.(a) In pure DMF; (b) 2.0; (c) 4.5; (d) 6.6 MPa. (e) Phase separation in reaction system at 6.6 MPa after reaction for 3 h.

Mentions: Cu3(BTC)2(H2O)3·xH2O (BTC=1,3,5-benzenetricarboxylate) is one of the most extensively explored MOFs for its various uses69373839. Herein we synthesized Cu3(BTC)2 in CO2-expanded N,N-dimethylformamide (DMF) at 30 °C, using copper(II) acetate monohydrate (Cu(OAc)2·H2O) and benzene-1,3,5-tricarboxylic acid (H3BTC) as MOF precursors. A certain amount of triethylamine was added into the reaction system to deprotonate the linker. Figure 1 shows the photographs of the reaction systems in pure DMF (Fig. 1a) and CO2-expanded DMF at different pressures (Fig. 1b–d). Evidently, the reaction system was expanded with the addition of CO2 and the volume expansion increased at higher pressure. After 3 h of reaction the stirring was stopped. The product separated out from the solvent naturally and precipitated at the bottom of the autoclave (Fig. 1e). Then the upper solvent was extracted by flowing CO2, and the product precipitated at the bottom of the autoclave was recovered and washed using ethanol.


Highly mesoporous metal-organic framework assembled in a switchable solvent.

Peng L, Zhang J, Xue Z, Han B, Sang X, Liu C, Yang G - Nat Commun (2014)

Photographs of MOF synthesis in CO2-expanded DMF.(a) In pure DMF; (b) 2.0; (c) 4.5; (d) 6.6 MPa. (e) Phase separation in reaction system at 6.6 MPa after reaction for 3 h.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4109014&req=5

f1: Photographs of MOF synthesis in CO2-expanded DMF.(a) In pure DMF; (b) 2.0; (c) 4.5; (d) 6.6 MPa. (e) Phase separation in reaction system at 6.6 MPa after reaction for 3 h.
Mentions: Cu3(BTC)2(H2O)3·xH2O (BTC=1,3,5-benzenetricarboxylate) is one of the most extensively explored MOFs for its various uses69373839. Herein we synthesized Cu3(BTC)2 in CO2-expanded N,N-dimethylformamide (DMF) at 30 °C, using copper(II) acetate monohydrate (Cu(OAc)2·H2O) and benzene-1,3,5-tricarboxylic acid (H3BTC) as MOF precursors. A certain amount of triethylamine was added into the reaction system to deprotonate the linker. Figure 1 shows the photographs of the reaction systems in pure DMF (Fig. 1a) and CO2-expanded DMF at different pressures (Fig. 1b–d). Evidently, the reaction system was expanded with the addition of CO2 and the volume expansion increased at higher pressure. After 3 h of reaction the stirring was stopped. The product separated out from the solvent naturally and precipitated at the bottom of the autoclave (Fig. 1e). Then the upper solvent was extracted by flowing CO2, and the product precipitated at the bottom of the autoclave was recovered and washed using ethanol.

Bottom Line: The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy.Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction.The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

View Article: PubMed Central - PubMed

Affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

ABSTRACT
The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

No MeSH data available.


Related in: MedlinePlus