In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) o...In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) or N-methyl- 2-pyrrolidone(NMP) on solvothermal synthesis of [Zn4O(BDC)3]8 were investigated through a combined DFT and experimental study. XRD and SEM showed that the absorbability of NMP in the pore of [Zn4O(BDC)3]8 was weaker than that of DMF. The thermal decomposition temperature of [Zn4O(BDC)3]8 synthesized in DMF was higher than that in NMP according to TG and FT-IR. In addition, the nitrogen sorption isotherms indicated that NMP improved gas sorption property of [Zn4O(BDC)3]8. The COSMO optimized calculations indicated that the total energy of Zn4O(BDC)3 in NMP was higher than that in DMF, and compared with non-solvent system, the charge of zinc atoms decreased and the charge value was the smallest in NMP. Furthermore, the interaction of DMF, NMP or DEF in [Zn4O(BDC)3]8 crystal model was calculated by DFT method. The results suggested that NMP should be easier to be removed from pore of materials than DMF from the point of view of energy state. It can be concluded that NMP was a favorable solvent to synthesize [Zn4O(BDC)3]8 and the microscopic mechanism was that the binding force between Zn4O(BDC)3 and NMP molecule was weaker than DMF.展开更多
Photocatalytic water splitting to generate hydrogen gas is an ideal solution for environmental pollution and unsustainable energy issues.In the past few decades,many efforts have been made to increase the efficiency o...Photocatalytic water splitting to generate hydrogen gas is an ideal solution for environmental pollution and unsustainable energy issues.In the past few decades,many efforts have been made to increase the efficiency of hydrogen production.One of the most important ways is to achieve light absorption in the visible range to improve the conversion efficiency of solar energy into chemical energy,but it still presents great challenges.We here predicted a novel organic film,which can be obtained by polymerizing HTAP molecules,as an ideal material for photocatalytic water splitting.Based on firstprinciples calculations and Born-Oppenheimer quantum molecular dynamic simulations,the metal-free two-dimensional nanomaterial has been proven to be structurally stable,with a direct band gap of 2.12 e V,which satisfies the requirement of light absorption in the visible range.More importantly,the conduction bands and valence bands completely engulf the redox potentials of water,making the film be a promising photocatalyst for water splitting.This construction method through the topological periodicity of organic molecules provides a design scheme for the photocatalyst for water splitting.展开更多
The pyrolysis of isopsoralen was studied by synchrotron vacuum ultraviolet photoionization mass spectrometry at low pressure. The pyrolysis products were detected at different photon energies, the ratios of products t...The pyrolysis of isopsoralen was studied by synchrotron vacuum ultraviolet photoionization mass spectrometry at low pressure. The pyrolysis products were detected at different photon energies, the ratios of products to precursor were measured at various pyrolysis temperatures. The experimental results demonstrate that the main pyrolysis products are primary CO and sequential CO elimination products （C10H602 and C9H60）. The decomposition channels of isopsoralen were also studied by the density functional theory, then rate constants for competing pathways were calculated by the transition state theory. The dominant decom- position channels of isopsoralen and the molecular structures for corresponding products were identified by combined experimental and theoretical studies.展开更多
基金Project(51104185)supported by the National Natural Science Foundation of ChinaProject(2010QZZD003)supported by the Key Project of Central South University of Fundamental Research Funds for the Central Universities of China
文摘In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) or N-methyl- 2-pyrrolidone(NMP) on solvothermal synthesis of [Zn4O(BDC)3]8 were investigated through a combined DFT and experimental study. XRD and SEM showed that the absorbability of NMP in the pore of [Zn4O(BDC)3]8 was weaker than that of DMF. The thermal decomposition temperature of [Zn4O(BDC)3]8 synthesized in DMF was higher than that in NMP according to TG and FT-IR. In addition, the nitrogen sorption isotherms indicated that NMP improved gas sorption property of [Zn4O(BDC)3]8. The COSMO optimized calculations indicated that the total energy of Zn4O(BDC)3 in NMP was higher than that in DMF, and compared with non-solvent system, the charge of zinc atoms decreased and the charge value was the smallest in NMP. Furthermore, the interaction of DMF, NMP or DEF in [Zn4O(BDC)3]8 crystal model was calculated by DFT method. The results suggested that NMP should be easier to be removed from pore of materials than DMF from the point of view of energy state. It can be concluded that NMP was a favorable solvent to synthesize [Zn4O(BDC)3]8 and the microscopic mechanism was that the binding force between Zn4O(BDC)3 and NMP molecule was weaker than DMF.
基金supported by the National Natural Science Foundation of China (No.21803031)the Natural Science Foundation of the Jiangsu Higher Education Institution of China (No.18KJB150022)Postdoctoral Science Foundation of China (No.2018M640438)。
文摘Photocatalytic water splitting to generate hydrogen gas is an ideal solution for environmental pollution and unsustainable energy issues.In the past few decades,many efforts have been made to increase the efficiency of hydrogen production.One of the most important ways is to achieve light absorption in the visible range to improve the conversion efficiency of solar energy into chemical energy,but it still presents great challenges.We here predicted a novel organic film,which can be obtained by polymerizing HTAP molecules,as an ideal material for photocatalytic water splitting.Based on firstprinciples calculations and Born-Oppenheimer quantum molecular dynamic simulations,the metal-free two-dimensional nanomaterial has been proven to be structurally stable,with a direct band gap of 2.12 e V,which satisfies the requirement of light absorption in the visible range.More importantly,the conduction bands and valence bands completely engulf the redox potentials of water,making the film be a promising photocatalyst for water splitting.This construction method through the topological periodicity of organic molecules provides a design scheme for the photocatalyst for water splitting.
文摘The pyrolysis of isopsoralen was studied by synchrotron vacuum ultraviolet photoionization mass spectrometry at low pressure. The pyrolysis products were detected at different photon energies, the ratios of products to precursor were measured at various pyrolysis temperatures. The experimental results demonstrate that the main pyrolysis products are primary CO and sequential CO elimination products （C10H602 and C9H60）. The decomposition channels of isopsoralen were also studied by the density functional theory, then rate constants for competing pathways were calculated by the transition state theory. The dominant decom- position channels of isopsoralen and the molecular structures for corresponding products were identified by combined experimental and theoretical studies.
