The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in orde...The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.展开更多
The development of robust photocatalytic systems is key to harvest the solar power for hydrogen production. In the current study, a series of aluminum-based porphyrinic metal organic frameworks (AlTCPP) with various m...The development of robust photocatalytic systems is key to harvest the solar power for hydrogen production. In the current study, a series of aluminum-based porphyrinic metal organic frameworks (AlTCPP) with various morphologies of bulk, carambola-like and nanosheets are synthesized with modulated layer thickness. Morphology-dependent photocatalytic activities in hydrogen production are witnessed and inversely correlate to the thickness of the Al-TCPP micro-platelets or nanosheets. Particularly, the exfoliated metal organic layers (MOLs) of Al-TCPP demonstrated a high hydrogen yield rate of 1.32×10^(4)μmol h^(-1)g^(-1)that is 21-fold of that from the bulk catalyst, as well as an exceptional TON of6704 that seldom seen in literature. Through comprehensive photochemical characterizations, the remarkable photocatalytic performance of Al-TCPP-MOL is attributed to the great charge separation efficiency and transfer kinetics endowed by the ultrathin 2D morphology with extended active surface area.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 22072101, 22075193, 51911540473)the Natural Science Research Project of Jiangsu Higher Education Institutions of China (18KJA480004)+2 种基金the Key Technology Initiative of Suzhou Municipal Science and Technology Bureau (SYG201934) Six Talent Peaks Project in Jiangsu Province (TD-XCL-006)the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutionsthe support from the Honorary Professor Program of Jiangsu Province。
文摘The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.
基金financially supported by National Natural Science Foundation of China (Nos. 22072101, 22075193, 51911540473)Natural Science Research Project of Jiangsu Higher Education Institutions of China (No. 18KJA480004)+2 种基金the Key Technology Initiative of Suzhou Municipal Science and Technology Bureau (No. SYG201934)Six Talent Peaks Project in Jiangsu Province (No. TD-XCL-006)Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions。
文摘The development of robust photocatalytic systems is key to harvest the solar power for hydrogen production. In the current study, a series of aluminum-based porphyrinic metal organic frameworks (AlTCPP) with various morphologies of bulk, carambola-like and nanosheets are synthesized with modulated layer thickness. Morphology-dependent photocatalytic activities in hydrogen production are witnessed and inversely correlate to the thickness of the Al-TCPP micro-platelets or nanosheets. Particularly, the exfoliated metal organic layers (MOLs) of Al-TCPP demonstrated a high hydrogen yield rate of 1.32×10^(4)μmol h^(-1)g^(-1)that is 21-fold of that from the bulk catalyst, as well as an exceptional TON of6704 that seldom seen in literature. Through comprehensive photochemical characterizations, the remarkable photocatalytic performance of Al-TCPP-MOL is attributed to the great charge separation efficiency and transfer kinetics endowed by the ultrathin 2D morphology with extended active surface area.
