Photocatalytic overall water splitting(OWS)into H_(2) and O_(2) has been recognized as a promising strategy to convert solar energy into chemical fuels.Herein,we proposed a new type of photocatalyst called“crystallin...Photocatalytic overall water splitting(OWS)into H_(2) and O_(2) has been recognized as a promising strategy to convert solar energy into chemical fuels.Herein,we proposed a new type of photocatalyst called“crystalline covalent molecular junction”and realized efficient OWS.A series of redox covalent organic framework(COF)catalysts(denoted as TTF-Ni COF,Bn-Ni COF,and TTF-TPE COF,respectively)were constructed,which finally achieved OWS using TTFNi COF without an additional photosensitizer or noble metal cocatalysts.Interestingly,the OWS efficiency was further enhanced when oxidized by I2 to obtain a radical cation containing I_(3)^(−)@TTF-Ni COF.Density functional theory(DFT)calculations illustrated that tetrathiafulvalene free radical(TTF^(·+))showed lower thermodynamic energy for H_(2)O oxidation compared to the original tetrathiafulvalene(TTF),thereby contributing to excellent OWS activity with a maximum H_(2) yield of 1.63mmol g^(−1) h^(−1) and O_(2) yield of 0.85mmol g^(−1) h^(−1).This work puts forward a practical strategy for designing redox covalent molecular junction catalysts,thus greatly enriching the possibilities of crystalline photocatalysts.展开更多
基金supported by the National Key R&D Program of China(grant no.2023YFA1507204)Major Research plan of the National Natural Science Foundation of China(grant no.92461310)+3 种基金National Natural Science Foundation of China(grant nos.22225109,22471082,and 22201083)Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization,China(grant no.2024B1212010011)the Guangdong Basic and Applied Basic Research Foundation(grant nos.2025B1515020049,2023A1515010779,and 2023A1515010928)the Guangzhou Basic and Applied Basic Research Fund Project(grant no.2024A04J2379).
文摘Photocatalytic overall water splitting(OWS)into H_(2) and O_(2) has been recognized as a promising strategy to convert solar energy into chemical fuels.Herein,we proposed a new type of photocatalyst called“crystalline covalent molecular junction”and realized efficient OWS.A series of redox covalent organic framework(COF)catalysts(denoted as TTF-Ni COF,Bn-Ni COF,and TTF-TPE COF,respectively)were constructed,which finally achieved OWS using TTFNi COF without an additional photosensitizer or noble metal cocatalysts.Interestingly,the OWS efficiency was further enhanced when oxidized by I2 to obtain a radical cation containing I_(3)^(−)@TTF-Ni COF.Density functional theory(DFT)calculations illustrated that tetrathiafulvalene free radical(TTF^(·+))showed lower thermodynamic energy for H_(2)O oxidation compared to the original tetrathiafulvalene(TTF),thereby contributing to excellent OWS activity with a maximum H_(2) yield of 1.63mmol g^(−1) h^(−1) and O_(2) yield of 0.85mmol g^(−1) h^(−1).This work puts forward a practical strategy for designing redox covalent molecular junction catalysts,thus greatly enriching the possibilities of crystalline photocatalysts.
