Compared to the conventional trial-and-error approach,computational prediction is becoming an increasingly prominent approach inthe discovery of covalent organic frameworks(COFs)with specific applications,yet it has b...Compared to the conventional trial-and-error approach,computational prediction is becoming an increasingly prominent approach inthe discovery of covalent organic frameworks(COFs)with specific applications,yet it has been rarely demonstrated.Herein,we em-ployed density functional theory(DFT)to pre-screen the electronic and optical properties of thiophene-based donor-acceptor(D-A)pairs simplified from their corresponding COF structures.Theoretical calculation illustrates the BMTB-BTTC with the highest number ofthiophene units is expected to exhibit the best photocatalytic performance for hydrogen production.According to calculation predic-tion,four COFs have been prepared and their photocatalytic activities have been experimentally validated.Interestingly,the corre-sponding BMTB-BTTC-COF shows the highest photocatalytic hydrogen production rate of 12.37 mmolg^(-1)·h^(-1) among the four COFs.Combining the calculation and experimental results,it has been proven that the photocatalytic activity can be fine-tuned by modulat-ing the number of thiophene units.Our study provides a new strategy for the rational design and regulation of D-A COFs to enhancephotocatalytic activity through computational prediction.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22371091,21975104,22150004,22201102,and 22302141)the Guangdong Major Project of Basic and Applied Research(No.2019B030302009)+4 种基金Zhejiang Provincial Natural Science Foundation of China(No.LY22E030008)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications(No.2020B121201005)the Postdoctoral Fellowship Program of CPSF(No.GZC20240598)China Postdoctoral Science Foundation(No.2024M751118)Q.G.is thankful for the financial support from Special Project for Peak Carbon Dioxide Emissions-Carbon Neutrality(21DZ1206900)from the Shanghai Municipal Science and Technology Commission.
文摘Compared to the conventional trial-and-error approach,computational prediction is becoming an increasingly prominent approach inthe discovery of covalent organic frameworks(COFs)with specific applications,yet it has been rarely demonstrated.Herein,we em-ployed density functional theory(DFT)to pre-screen the electronic and optical properties of thiophene-based donor-acceptor(D-A)pairs simplified from their corresponding COF structures.Theoretical calculation illustrates the BMTB-BTTC with the highest number ofthiophene units is expected to exhibit the best photocatalytic performance for hydrogen production.According to calculation predic-tion,four COFs have been prepared and their photocatalytic activities have been experimentally validated.Interestingly,the corre-sponding BMTB-BTTC-COF shows the highest photocatalytic hydrogen production rate of 12.37 mmolg^(-1)·h^(-1) among the four COFs.Combining the calculation and experimental results,it has been proven that the photocatalytic activity can be fine-tuned by modulat-ing the number of thiophene units.Our study provides a new strategy for the rational design and regulation of D-A COFs to enhancephotocatalytic activity through computational prediction.
