Researchers Reveal Solvatomorphism Influence of Porous Organic Cage on C2H2/CO2 Separation (Chemistry)

Porous organic cages (POCs) are discrete, covalently linked molecules with intrinsic cavities. The porous nature of POCs enables them to be nanoscale reaction vessels for catalysis, hosts for different guest molecules, and adsorbents for gas storage and separation. 

POCs materials exhibit solvatomorphs via altering their crystallographic packing in the solid state, but the investigation of real gas mixture separation by porous materials with such a behavior is still very rare. 

In a study published in ACS Appl. Mater. Interfaces, the group led by Prof. YUAN Daqiang from Fujian Institute of Research on the Structure of Matter of the Chinese Academy of Sciences reported that a lantern-shaped calix[4]resorcinarene-based porous organic cage (POC, namely, CPOC-101) can exhibit eight distinct solid-state solvatomorphs via crystallization in different solvents, and this POC solvatomorphism strongly influences their gas sorption capacities and separation abilities. 

The researchers found that the apparent Brunauer-Emmett-Teller (BET) surface area determined by nitrogen gas sorption at 77 K for CPOC-101α crystallized from toluene/chloroform is up to 406 m2 g-1, which is much larger than that of the rest of CPOC-101 solvatomorphs with BET values less than 40 m2 g-1.  

They also found that C2H2 and CO2 adsorbed capacities, in addition to the C2H2/CO2 separation ability at room temperature for CPOC-101α, are superior to those of CPOC-101β crystalized from nitrobenzene, the representative of POC solvatomorphs with low BET surface areas.  

To understand the mechanism of the higher affinity toward C2H2 over CO2 within CPOC-101, the researchers computed the interaction energies between the optimized cage host and gas guests by the first-principles dispersion-corrected density functional theory (DFT-D) calculations.  

The hydrogen-bond number (6 for C2H2 and 5 for CO2), the average hydrogen-bond length (3.12 Å for C2H2 and 3.26 Å for CO2), and the calculated interaction enthalpies highly indicated that the host-guest interaction between the C2H2 molecule and CPOC-101 is much stronger than that of CO2

This study reveals the possibility of adjusting gas sorption and separation properties of POC materials by controlling their solvatomorphs. 

Featured image: CPOC-101 for C2H2/CO2 separation. (Image by Prof. YUAN’s group)  


Provided by Chinese Academy of Sciences

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