Supramolecular frameworks(SMFs)are famous for their fascinating structure and abundant porosity;however,poor crystalline stability in water severely limits their applications.Herein,an anchoringpolymerization strategy...Supramolecular frameworks(SMFs)are famous for their fascinating structure and abundant porosity;however,poor crystalline stability in water severely limits their applications.Herein,an anchoringpolymerization strategy was developed under mild conditions to modulate the surface microenvironment of SMFs.The process-tracking experiment demonstrated that toluene diisocyanate(TDI)was anchored on the surface of SMF-BDC-NH_(2)before chain polymerization was initiated between TDI by introducing trace amounts of water.The glue-like polyurea armor on the surface of SMF-BDC-NH_(2)@PTDI endowed it with a water contact angle of 131.3°,and it can maintain good crystallinity and a porous structure even when immersed in water for 24 hours.SMF-BDC-NH_(2)@PTDI was proved to selectively adsorb cationic dyes,and no significant loss was detected after 5 runs,whereas the pristine material lost crystallinity and adsorption performance immediately after regeneration.The dynamic breakthrough experiment showed that SMF-BDC-NH_(2)@PTDI had an adsorption capacity of 124 mg g^(-1),positioning it among the best materials of its kind.Suitable pore size and charge interactions are proved to be the main driving forces for selective adsorption.This work may open a path to modulation of the surface microenvironment of SMFs to maintain crystalline stability and enable advanced applications in water treatment.展开更多
基金supported by the Natural Science Foundation of Jiangsu Province(BK20231270)the National Science Fund for Distinguished Young Scholars(22125804).
文摘Supramolecular frameworks(SMFs)are famous for their fascinating structure and abundant porosity;however,poor crystalline stability in water severely limits their applications.Herein,an anchoringpolymerization strategy was developed under mild conditions to modulate the surface microenvironment of SMFs.The process-tracking experiment demonstrated that toluene diisocyanate(TDI)was anchored on the surface of SMF-BDC-NH_(2)before chain polymerization was initiated between TDI by introducing trace amounts of water.The glue-like polyurea armor on the surface of SMF-BDC-NH_(2)@PTDI endowed it with a water contact angle of 131.3°,and it can maintain good crystallinity and a porous structure even when immersed in water for 24 hours.SMF-BDC-NH_(2)@PTDI was proved to selectively adsorb cationic dyes,and no significant loss was detected after 5 runs,whereas the pristine material lost crystallinity and adsorption performance immediately after regeneration.The dynamic breakthrough experiment showed that SMF-BDC-NH_(2)@PTDI had an adsorption capacity of 124 mg g^(-1),positioning it among the best materials of its kind.Suitable pore size and charge interactions are proved to be the main driving forces for selective adsorption.This work may open a path to modulation of the surface microenvironment of SMFs to maintain crystalline stability and enable advanced applications in water treatment.
