Imine-linked covalent organic frameworks(COFs)provide distinctive prospects for promoting photocatalytic H_(2)O_(2) production,yet the intricate involvement of imine-derived linkages chemistry under light irradiation ...Imine-linked covalent organic frameworks(COFs)provide distinctive prospects for promoting photocatalytic H_(2)O_(2) production,yet the intricate involvement of imine-derived linkages chemistry under light irradiation remains incompletely elucidated.Here,imine-linked COF-LZU1 demonstrates a visible light-driven H_(2)O_(2) evolution rate of 387μmol g^(-1)h^(-1),particularly,negligible dependence on the sacrificial agents.By virtue of electron paramagnetic spectroscopy and solid-state nuclear magnetic resonance,we experimentally tracked the structure evolution and identified its autooxidation to Wurster's salt mimics under the photocatalytic conditioning.This finding coincides with the radical anion-O_(2)^(-)-governed reaction pathway and is further rationalized with additional theoretical calculations.This study provides insights into both photophysical/photochemical aspects over the imine-linkage structure.展开更多
Imine-linked covalent organic framework on amino functionalized silicon substrate was constructed via a step-wise reaction between 1,3,5-benzenetricarboxaldehyde and 1,4-diaminobenzene.The obtained material was used a...Imine-linked covalent organic framework on amino functionalized silicon substrate was constructed via a step-wise reaction between 1,3,5-benzenetricarboxaldehyde and 1,4-diaminobenzene.The obtained material was used as biosensor for bovine serum albumin(BSA)adsorption and probe DNA immobilization,which extended the application of covalent organic frameworks(COFs)to a new field.展开更多
Conjugated linear polymers are promising metal-free photocatalysts for visible-light-driven photocatalytic water disinfection,but it was still bottlenecked by the insufficient photogenerated charge separation and tran...Conjugated linear polymers are promising metal-free photocatalysts for visible-light-driven photocatalytic water disinfection,but it was still bottlenecked by the insufficient photogenerated charge separation and transport(CST)process.Herein,we obtained the highly crystalline imine-linked conjugated linear poly-mer(ODA-BPAH)with a greatly enhanced CST process.The highly crystalline ODA-BPAH exhibited excel-lent broad-spectrum water disinfection efficiency up to 99.99999%in 1 h,which is among the reported highest of state-of-the-art photocatalysts.The crystallinity of ODA-BPAH was regulated by simply turn-ing the solvent and the experiment results revealed that the ODA-BPAH with high crystallinity exhibited higher internal electric field strength and photocatalytic performance than that with low crystallinity,which indicates that higher crystallinity in linear conjugated polymers contributes to superior CST ef-ficiency as well as the generation of reactive oxygen species.This work highlights the impact of poly-mer crystallinity on the internal electric field and proves that linear poly-imine could be a new type of promising metal-free photocatalyst for water treatment.展开更多
基金This work was supported by the National Natural Science Foundation of China(22002013)the Fundamental Research Funds for the Central Universities(DUT22LAB602)+1 种基金Liao Ning Revitalization Talents Program(XLYC2008032)China Postdoctoral Science Foundation(Grant No.2023M740496).
文摘Imine-linked covalent organic frameworks(COFs)provide distinctive prospects for promoting photocatalytic H_(2)O_(2) production,yet the intricate involvement of imine-derived linkages chemistry under light irradiation remains incompletely elucidated.Here,imine-linked COF-LZU1 demonstrates a visible light-driven H_(2)O_(2) evolution rate of 387μmol g^(-1)h^(-1),particularly,negligible dependence on the sacrificial agents.By virtue of electron paramagnetic spectroscopy and solid-state nuclear magnetic resonance,we experimentally tracked the structure evolution and identified its autooxidation to Wurster's salt mimics under the photocatalytic conditioning.This finding coincides with the radical anion-O_(2)^(-)-governed reaction pathway and is further rationalized with additional theoretical calculations.This study provides insights into both photophysical/photochemical aspects over the imine-linkage structure.
基金This work was financially supported by the National Natural Science Foundation of China(No.21104070)the School Doctorial Foundation of Zhengzhou University of Light Industry(No.2011BSJJ011).
文摘Imine-linked covalent organic framework on amino functionalized silicon substrate was constructed via a step-wise reaction between 1,3,5-benzenetricarboxaldehyde and 1,4-diaminobenzene.The obtained material was used as biosensor for bovine serum albumin(BSA)adsorption and probe DNA immobilization,which extended the application of covalent organic frameworks(COFs)to a new field.
基金This work was financially supported by the Liaoning Revital-ization Talents Program(No.1808013)the Shenyang National Laboratory for Materials Science.The authors thank Mr.Long Guan and Mr.Zhiyong Yang from Shenyang Dequan Instrument and Equipment Sales Co.,Ltd.for the Fluorescence microscope analysis and Mr.Jilong Gao from Shiyanjia Lab(www.shiyanjia.com)for the ss NMR analysis.
文摘Conjugated linear polymers are promising metal-free photocatalysts for visible-light-driven photocatalytic water disinfection,but it was still bottlenecked by the insufficient photogenerated charge separation and transport(CST)process.Herein,we obtained the highly crystalline imine-linked conjugated linear poly-mer(ODA-BPAH)with a greatly enhanced CST process.The highly crystalline ODA-BPAH exhibited excel-lent broad-spectrum water disinfection efficiency up to 99.99999%in 1 h,which is among the reported highest of state-of-the-art photocatalysts.The crystallinity of ODA-BPAH was regulated by simply turn-ing the solvent and the experiment results revealed that the ODA-BPAH with high crystallinity exhibited higher internal electric field strength and photocatalytic performance than that with low crystallinity,which indicates that higher crystallinity in linear conjugated polymers contributes to superior CST ef-ficiency as well as the generation of reactive oxygen species.This work highlights the impact of poly-mer crystallinity on the internal electric field and proves that linear poly-imine could be a new type of promising metal-free photocatalyst for water treatment.
