Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an eff...Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.展开更多
Covalent organic frameworks(COFs)have garnered increasing attention as promising electrode materials for sodium-ion batteries(SIBs)due to their ordered backbones,uniform pore sizes,and high surface areas.However,they ...Covalent organic frameworks(COFs)have garnered increasing attention as promising electrode materials for sodium-ion batteries(SIBs)due to their ordered backbones,uniform pore sizes,and high surface areas.However,they also face challenges,including low capacity,unsatisfactory rate performance,and limited cycling stability,which pose the primary obstacles to their practical use.Herein,a pyrenoimidazole-based COF,denoted as PyIm-COF,has been synthesized as a novel electrode material for highperformance SIBs using an efficient synthetic strategy.With extended fully conjugated backbones and readily accessible redox-active sites,PyIm-COF demonstrates remarkable high-rate performance,delivering around 250 m Ah g^(−1)and excellent cycling stability,retaining 97.2%of its capacity even after 2500 cycles at 5 A g^(−1),which is higher than that of most previously reported COF-based SIBs.This work provides valuable insights into the development of nitrogen-rich conjugated COF electrode materials for rechargeable SIBs.展开更多
Star shape bridged pillar[5]arene trimer(C3-PLT) based on benzene-1,3,5-tricarboxamide(BTAs) was successfully synthesized,which exhibited outstanding guest responsive morphology transition properties.The morphology ti...Star shape bridged pillar[5]arene trimer(C3-PLT) based on benzene-1,3,5-tricarboxamide(BTAs) was successfully synthesized,which exhibited outstanding guest responsive morphology transition properties.The morphology tining studies was efficiently achieved with the addition of competitive guest molecules G1 and G2 by various self-assembly mechanisms.C3-PLT itself displays nanofiber morphology through H-type π-π stacking,and this nanofiber morphology can be completely transformed into spherical vesicles by host-guest interaction Gl,while upon addition of G2 into C3-PLT by means of "exo-wall" electron-transfer interactions,sheet superstructures can be observed.SEM,~1 H NMR,DOSY,fluorescence spectroscopy,and viscosity have verified the formation of supramolecular polymers and morphological transitions between C3-PLT with both guests.展开更多
Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materia...Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materials. Herein, we report an effective synthetic protocol to fabricate a new pyrylium-containing porous organic polymers(POPs), named TMP-P, via Knoevenagel condensation with 2,4,6-trimethylpyrylium salt(TMP) as the key building block and 1,4-phthalaldehyde as the linker. The resulting ionic polymer TMPP exhibited efficient visible-light-driven heterogeneous photodegradation of Rhodamine B, owing to the presence of wide visible light absorption and a narrow optical band gap triggered pyrylium core in the framework.展开更多
Carbazole-based conjugated microporous polymers(CMPs)as a new type of advanced porous material have created tremendous research curiosities in the area of photocatalysis.Besides,introducing boron-containing dyes into ...Carbazole-based conjugated microporous polymers(CMPs)as a new type of advanced porous material have created tremendous research curiosities in the area of photocatalysis.Besides,introducing boron-containing dyes into the CMPs framework was rare but will be rather promising due to their unique properties,including strong electron-accepting capability,efficient catalytic behaviour,significant absorption coefficient and high quantum.Herein,we rationally designed and prepared two new CMPs,i.e.Cz-BF_(2)-CMP and Cz-BPh2-CMP with the combination of carbazole and boron-containing dye as electron donor and acceptor motifs,respectively.Due to the efficient D-A effect between carbazole and boron-dye which not only accelerated the interfacial charge transfer efficiency but also improved the separation capability of photogenerated electron-hole pairs,both CMPs exhibited excellent photocatalytic performances in organic transformations such as green synthesis of benzimidazole in aqueous solution and aerobic oxidation of thioether in EtOH.展开更多
基金the National Natural Science Foundation of China(No.U1808210)the Natural Science Foundation of Liaoning province(No.2019-MS-046).
文摘Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.
基金the Natural Science Foundation of Liaoning province(grant no.2019-MS-046)W.Zhang thanks the University of Colorado Boulder for financial support of this work+1 种基金W.Huang acknowledges the support from the National Natural Science Foundation of China(grant no.21875206)The authors acknowledge the assistance of the Dalian University of Technology Instrumental Analysis Center.
文摘Covalent organic frameworks(COFs)have garnered increasing attention as promising electrode materials for sodium-ion batteries(SIBs)due to their ordered backbones,uniform pore sizes,and high surface areas.However,they also face challenges,including low capacity,unsatisfactory rate performance,and limited cycling stability,which pose the primary obstacles to their practical use.Herein,a pyrenoimidazole-based COF,denoted as PyIm-COF,has been synthesized as a novel electrode material for highperformance SIBs using an efficient synthetic strategy.With extended fully conjugated backbones and readily accessible redox-active sites,PyIm-COF demonstrates remarkable high-rate performance,delivering around 250 m Ah g^(−1)and excellent cycling stability,retaining 97.2%of its capacity even after 2500 cycles at 5 A g^(−1),which is higher than that of most previously reported COF-based SIBs.This work provides valuable insights into the development of nitrogen-rich conjugated COF electrode materials for rechargeable SIBs.
基金the financial support from the National Natural Science Foundation of China(No.21206016)the Fundamental Research Funds for the Central Universities(No.DUT17LK07)the Natural Science Foundation of Liaoning Province(No.2019-MS-046)。
文摘Star shape bridged pillar[5]arene trimer(C3-PLT) based on benzene-1,3,5-tricarboxamide(BTAs) was successfully synthesized,which exhibited outstanding guest responsive morphology transition properties.The morphology tining studies was efficiently achieved with the addition of competitive guest molecules G1 and G2 by various self-assembly mechanisms.C3-PLT itself displays nanofiber morphology through H-type π-π stacking,and this nanofiber morphology can be completely transformed into spherical vesicles by host-guest interaction Gl,while upon addition of G2 into C3-PLT by means of "exo-wall" electron-transfer interactions,sheet superstructures can be observed.SEM,~1 H NMR,DOSY,fluorescence spectroscopy,and viscosity have verified the formation of supramolecular polymers and morphological transitions between C3-PLT with both guests.
基金financial support from the Natural Science Foundation of Liaoning Province (No. 2019-MS-046)。
文摘Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materials. Herein, we report an effective synthetic protocol to fabricate a new pyrylium-containing porous organic polymers(POPs), named TMP-P, via Knoevenagel condensation with 2,4,6-trimethylpyrylium salt(TMP) as the key building block and 1,4-phthalaldehyde as the linker. The resulting ionic polymer TMPP exhibited efficient visible-light-driven heterogeneous photodegradation of Rhodamine B, owing to the presence of wide visible light absorption and a narrow optical band gap triggered pyrylium core in the framework.
基金We are grateful for financial support from the National Natural Science Foundation of China(No.U1808210)the Natural Science Foundation of Liaoning Province(No.2019-MS-046)the Open Sharing Fund for the Large-scale Instruments and Equipment of Dalian University of Technology(Nos.DUTKFJJ2021086 and DUTKFJJ2021122).
文摘Carbazole-based conjugated microporous polymers(CMPs)as a new type of advanced porous material have created tremendous research curiosities in the area of photocatalysis.Besides,introducing boron-containing dyes into the CMPs framework was rare but will be rather promising due to their unique properties,including strong electron-accepting capability,efficient catalytic behaviour,significant absorption coefficient and high quantum.Herein,we rationally designed and prepared two new CMPs,i.e.Cz-BF_(2)-CMP and Cz-BPh2-CMP with the combination of carbazole and boron-containing dye as electron donor and acceptor motifs,respectively.Due to the efficient D-A effect between carbazole and boron-dye which not only accelerated the interfacial charge transfer efficiency but also improved the separation capability of photogenerated electron-hole pairs,both CMPs exhibited excellent photocatalytic performances in organic transformations such as green synthesis of benzimidazole in aqueous solution and aerobic oxidation of thioether in EtOH.