It is a prospective strategy to produce sustainable energy by photocatalytic overall water splitting(POWS).This work aims to develop a simple method for integrating a donor-acceptor system into polymeric car-bon nitri...It is a prospective strategy to produce sustainable energy by photocatalytic overall water splitting(POWS).This work aims to develop a simple method for integrating a donor-acceptor system into polymeric car-bon nitride(PCN)structure,which could accelerate the charge separation significantly.In the as-prepared photocatalyst(COCNT),carbon and oxygen were successfully incorporated into the framework of PCN,and the chemical environment of C and O was well probed by X-ray absorption near-edge structure(XANES)and X-ray photoelectron spectroscopy(XPS).It showed that the C-containing and O-containing segments of COCNT played the role of a donor,while the heptazine part played the role of an acceptor.In addition,Density-functional-theory(DFT)calculations confirmed the spatial split of the highest occupied molec-ular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)for promoting charge separation.Impressively,COCNT could efficiently split pure water to generate hydrogen and oxygen.And,the photo-catalytic hydrogen evolution rate over COCNT(1550.9μmol g^(-1)h^(-1))is about 17-fold higher than that of PCN.Finally,we proposed a possible photocatalytic mechanism to explain the above results.展开更多
Although a series of trifluoromethoxy(OCF_(3))reagents have been developed,they have rarely been employed as bifunctional reagents,because their leaving groups typically dissociate as either inactive or poorly reactiv...Although a series of trifluoromethoxy(OCF_(3))reagents have been developed,they have rarely been employed as bifunctional reagents,because their leaving groups typically dissociate as either inactive or poorly reactive fragments.By elegant structure modification and selection of activation strategy,we herein present a bifunctional N-OCF_(3)reagent,which acts as both nitrogen radical source and OCF_(3)−donor.This innovative reagent enabled direct styrenes amidotrifluoromethoxylation,overcoming limitations of conventional methods for synthesizingβ-amino-OCF_(3)scaffolds.Besides,the method showed a broad scope and compatibility with complex bioactive molecules.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21703097 and 21972172)South-ern University of Science and Technology(SUSTech)start fund through the Shenzhen Peacock Talent program,the Shenzhen Ba-sic Research Fund project(No.JCYJ20150507170334573)the Guangdong Innovative and Entrepreneurial Research Team Program(No.2016ZT06N532).
文摘It is a prospective strategy to produce sustainable energy by photocatalytic overall water splitting(POWS).This work aims to develop a simple method for integrating a donor-acceptor system into polymeric car-bon nitride(PCN)structure,which could accelerate the charge separation significantly.In the as-prepared photocatalyst(COCNT),carbon and oxygen were successfully incorporated into the framework of PCN,and the chemical environment of C and O was well probed by X-ray absorption near-edge structure(XANES)and X-ray photoelectron spectroscopy(XPS).It showed that the C-containing and O-containing segments of COCNT played the role of a donor,while the heptazine part played the role of an acceptor.In addition,Density-functional-theory(DFT)calculations confirmed the spatial split of the highest occupied molec-ular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)for promoting charge separation.Impressively,COCNT could efficiently split pure water to generate hydrogen and oxygen.And,the photo-catalytic hydrogen evolution rate over COCNT(1550.9μmol g^(-1)h^(-1))is about 17-fold higher than that of PCN.Finally,we proposed a possible photocatalytic mechanism to explain the above results.
基金supported by the National Key Research and Development Program of China(grant no.2021YFF0701700)the National Natural Science Foundation of China(NFSC)(grant nos.21925105 and 92156001)+1 种基金the Natural Science Foundation of Tianjin,China(grant no.24JCZDJC00700)the Haihe Laboratory of Sustainable Chemical Transformations,China,and the Fundamental Research Funds for the Central Universities,China.
文摘Although a series of trifluoromethoxy(OCF_(3))reagents have been developed,they have rarely been employed as bifunctional reagents,because their leaving groups typically dissociate as either inactive or poorly reactive fragments.By elegant structure modification and selection of activation strategy,we herein present a bifunctional N-OCF_(3)reagent,which acts as both nitrogen radical source and OCF_(3)−donor.This innovative reagent enabled direct styrenes amidotrifluoromethoxylation,overcoming limitations of conventional methods for synthesizingβ-amino-OCF_(3)scaffolds.Besides,the method showed a broad scope and compatibility with complex bioactive molecules.
基金supported by the Project of the National Nature Science Foundation of China(20531060 , 20418001 , 20473102)the National Basic Research 973 Program of China (2005CB623602 and 2006CB806201)National Center for Nanoscience and Technology,China
