4.8 Article

Unusual Missing Linkers in an Organosulfonate-Based Primitive-Cubic (pcu)-Type Metal-Organic Framework for CO2 Capture and Conversion under Ambient Conditions

Journal

ACS CATALYSIS
Volume 8, Issue 3, Pages 2519-2525

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b04189

Keywords

metal-organic frameworks; sulfonate; CO2 fixation; heterogeneous catalysis; alkyne activation

Funding

  1. National Natural Science Foundation of China [51772217, 21501136]
  2. Recruitment of Global Youth Experts by China
  3. Fundamental Research Funds for the Central Universities
  4. Science & Technology Commission of Shanghai Municipality [14DZ2261100]

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A noninterpenetrated organosulfonate-based metal-organic framework (MOF) with a defective primitive-cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (similar to 43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into alpha-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.

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