A Microporous Hydrogen Bonded Organic Framework for Highly Selective Separation of Carbon Dioxide over Acetylene

The separation of acetylene (C₂ H₂ ) from carbon dioxide (CO₂ ) is a very important but challenging task due to their similar molecular dimensions and physical properties. In terms of porous adsorbents for this separation, the CO₂ -selective porous materials are superior to the C₂ H₂ -selective ones because of the cost- and energy-efficiency but have been rarely achieved. Herein we report our unexpected discovery of the first hydrogen bonded organic framework (HOF) constructed from a simple organic linker 2,4,6-tri(1H-pyrazol-4-yl)pyridine (PYTPZ) (termed as HOF-FJU-88) as the highly CO₂ -selective porous material. HOF-FJU-88 is a two-dimensional HOFs with a pore pocket of about 7.6 Å. The activated HOF-FJU-88 takes up a high amount of CO₂ (59.6 cm³  g^-1 ) at ambient conditions with the record IAST selectivity of 1894. Its high performance for the CO₂ /C₂ H₂ separation has been further confirmed through breakthrough experiments, in situ diffuse reflectance infrared spectroscopy and molecular simulations.