Interfacial charge transfer and active sites play important roles in the performance of heterogeneousphotocatalysts. Reticular chemistry in covalent organic frameworks (COFs) allows the construction of isomericarchite...Interfacial charge transfer and active sites play important roles in the performance of heterogeneousphotocatalysts. Reticular chemistry in covalent organic frameworks (COFs) allows the construction of isomericarchitectures made of different donor and acceptor monomers for tuning the charge transferdynamics and active sites. Herein, five D-A dual-pore COFs were prepared from the reaction of naphthalene-2,6-diamine (electron donor) with different tetraaldehyde electron acceptors. Experimental resultsdisclosed that linker engineering, by changing the conjugation systems using heteroatoms of benzooxadiazole,benzothiadiazole, benzoselenadiazole, naphthothiadiazole, and naphthoselenadiazole, tuned theelectron-accepting capacity of the corresponding D-A COFs. Among the five samples, the naphthothiadiazole-derived COF demonstrated optimal charge transfer and active sites, exhibiting the highest hydrogenevolution rate of ca. 35 mmol g^(-1) h^(-1) in the presence of 3 wt% Pt under visible-light irradiation(>420 nm). This work illustrates linker engineering as a strategy for the simultaneous adjustment of interfacialcharge transfer and active sites to enhance the hydrogen generation efficiency, offering new vigorto develop the COF photocatalysts on the basis of reticular synthesis.展开更多
基金supported by the Natural Science Foundation of China(No.22261132512,22235001,22175020,and 22131005)Xiaomi Young Scholar Program,and University of Science and Technology Beijing.
文摘Interfacial charge transfer and active sites play important roles in the performance of heterogeneousphotocatalysts. Reticular chemistry in covalent organic frameworks (COFs) allows the construction of isomericarchitectures made of different donor and acceptor monomers for tuning the charge transferdynamics and active sites. Herein, five D-A dual-pore COFs were prepared from the reaction of naphthalene-2,6-diamine (electron donor) with different tetraaldehyde electron acceptors. Experimental resultsdisclosed that linker engineering, by changing the conjugation systems using heteroatoms of benzooxadiazole,benzothiadiazole, benzoselenadiazole, naphthothiadiazole, and naphthoselenadiazole, tuned theelectron-accepting capacity of the corresponding D-A COFs. Among the five samples, the naphthothiadiazole-derived COF demonstrated optimal charge transfer and active sites, exhibiting the highest hydrogenevolution rate of ca. 35 mmol g^(-1) h^(-1) in the presence of 3 wt% Pt under visible-light irradiation(>420 nm). This work illustrates linker engineering as a strategy for the simultaneous adjustment of interfacialcharge transfer and active sites to enhance the hydrogen generation efficiency, offering new vigorto develop the COF photocatalysts on the basis of reticular synthesis.
