Using hydrogen-bonded organic frameworks(HOFs)as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials.This study pre...Using hydrogen-bonded organic frameworks(HOFs)as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials.This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment.By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H_(4)TBAPy)as the monomer,a pyrene-based hydrogen-bonded organic framework(PFC-1)with a microporous structure was successfully prepared.Compared with monomer H_(4)TBAPy,due to the exciton effect and the interlayer confinement of HOFs,the singlet oxygen(1O_(2))production efficiency is significantly improved,which has great potential in photocatalytic oxidation reactions.Subsequently,the practicality of PFC-1 as a photocatalyst was studied,and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency,indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions.The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation,hence expanding the potential applications of HOFs materials within the realm of photocatalysis.展开更多
To develop porous organic frameworks,precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important.From these points of view,porous mo...To develop porous organic frameworks,precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important.From these points of view,porous molecular crystals formed through reversible intermolecular hydrogen bonds,such as;hydrogen-bonded organic frameworks(HOFs),can provide deep insight because of their high crystallinity,affording single-crystalline X-ray diffraction analysis.In this study,we demonstrate that the stacking manner of hydrogen-bonded hexagonal network(HexNet)sheets can be controlled by synchronizing a homological triangular macrocyclic tecton and a hydrogen-bonded cyclic supramolecular synthon called the phenylene triangle.A structure of the resultant HOF was crystallographically characterized and revealed to have a large channel aperture of 2.4 nm.The HOF also shows thermal stability up to 290°C,which is higher than that of the conventional HexNet frameworks.展开更多
基金financial support from the National Natural Science Foundation of China(No.52205210)the Natural Science Foundation of Shandong Province(Nos.ZR2020MB018,ZR2022QE033 and ZR2021QB049)。
文摘Using hydrogen-bonded organic frameworks(HOFs)as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials.This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment.By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H_(4)TBAPy)as the monomer,a pyrene-based hydrogen-bonded organic framework(PFC-1)with a microporous structure was successfully prepared.Compared with monomer H_(4)TBAPy,due to the exciton effect and the interlayer confinement of HOFs,the singlet oxygen(1O_(2))production efficiency is significantly improved,which has great potential in photocatalytic oxidation reactions.Subsequently,the practicality of PFC-1 as a photocatalyst was studied,and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency,indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions.The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation,hence expanding the potential applications of HOFs materials within the realm of photocatalysis.
基金KAKENHI(JP21H01919,JP21K18961,JP22H05461,and JP23H04029)from MEXT/JSPS,JapanI.H.thanks the Iketani Science and Technology Foundation and the Hoansha Foundation for their financial support.I.H.thanks the Multidisciplinary Research Laboratory System for Future Developments(MRL),Graduate School of Engineering Science,Osaka UniversityWe thank Ms.R.Miyake for HR−MS analysis.X-ray diffraction data were collected at BL40XU in SPring-8 with approval of JASRI(proposal nos.2021A1080,2022B1151,and 2023A1264).
文摘To develop porous organic frameworks,precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important.From these points of view,porous molecular crystals formed through reversible intermolecular hydrogen bonds,such as;hydrogen-bonded organic frameworks(HOFs),can provide deep insight because of their high crystallinity,affording single-crystalline X-ray diffraction analysis.In this study,we demonstrate that the stacking manner of hydrogen-bonded hexagonal network(HexNet)sheets can be controlled by synchronizing a homological triangular macrocyclic tecton and a hydrogen-bonded cyclic supramolecular synthon called the phenylene triangle.A structure of the resultant HOF was crystallographically characterized and revealed to have a large channel aperture of 2.4 nm.The HOF also shows thermal stability up to 290°C,which is higher than that of the conventional HexNet frameworks.
