Charged Covalent Triazine Frameworks for CO2Capture and Conversion.
The quest for the development of new porous materials addressing both CO2capture from various sources and its conversion into useful products is a very active research area and also critical in order to develop a more sustainable and environmentally-friendly society. Here, we present the first charged covalent triazine framework (cCTF) prepared by simply heating nitrile functionalized dicationic viologen derivatives under ionothermal reaction conditions using ZnCl2as both solvent and trimerization catalyst. It has been demonstrated that the surface area, pore volume/size of cCTFs can be simply controlled by varying the synthesis temperature and the ZnCl2content. Specifically, increasing the reaction temperature led to controlled increase in the mesopore content and facilitated the formation of hierarchical porosity, which is critical to ensure efficient mass transport within porous materials. The resulting cCTFs showed high specific surface areas up to 1247 m2g-1, and high physicochemical stability. The incorporation of ionic functional moieties to porous organic polymers improved substantially their CO2affinity (up to 133 mg g-1, at 1 bar and 273 K) and transformed them into hierarchically porous organocatalysts for CO2conversion. More importantly, the ionic nature of cCTFs, homogeneous charge distribution together with hierarchical porosity offered a perfect platform for the catalytic conversion of CO2into cyclic carbonates in the presence of epoxides through an atom economy reaction in high yields and exclusive product selectivity. These results clearly demonstrate the promising aspect of incorporation of charged units into the porous organic polymers for the development of highly efficient porous organocatalysts for CO2capture and fixation.
Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 305-701, Republic of Korea.
Onur
O
Buyukcakir
Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 305-701, Republic of Korea.
Sang Hyun
SH
Je
Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 305-701, Republic of Korea.
Siddulu Naidu
SN
Talapaneni
Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 305-701, Republic of Korea.
Daeok
D
Kim
Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 305-701, Republic of Korea.|Department of Chemistry, KAIST , Daejeon 305-701, Republic of Korea.
Ali
http://orcid.org/0000-0002-4760-1546
A
Coskun
CO2 fixation; charged porous polymers; hierarchical porosity; ionic networks; ionothermal synthesis