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
Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium c...Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium chloride solution containing lithium was illustrated based on the experimental results, and the effect of lithium on the crystallization of magnesium was clarified. The results of X-ray diffraction（XRD）, scanning election microscope（SEM）, Fourier transform infrared spectroscopy（FTIR）, thermogravimetry analysis（TGA） and laser particle size analysis indicate that the effect of lithium is not obvious on the crystal phase and morphology of the products. But the XRD relative intensity of（001） surface of magnesium hydroxide declines, the specific surface area reduces apparently and the additive mass of lithium affects the heat loss rates of precipitations obviously. Quantum chemical calculations on the interactional systems of Mg（H2O）2＋6 and Li（H2O）＋4 were performed using B3LYP/6-311 G basis set. The results show that when the distance of Mg2＋ and Li＋ is 7-10 , the interaction energy is high and the trend of solvation is strong, which would make hydroxide ions easier to combine with hydrogen ions in ammonia precipitation process. And the absolute value of solvation free energy reduces significantly in MgCl2 solution（1 mol/L） containing lithium ion.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Projects(51104185,51134007)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Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium chloride solution containing lithium was illustrated based on the experimental results, and the effect of lithium on the crystallization of magnesium was clarified. The results of X-ray diffraction（XRD）, scanning election microscope（SEM）, Fourier transform infrared spectroscopy（FTIR）, thermogravimetry analysis（TGA） and laser particle size analysis indicate that the effect of lithium is not obvious on the crystal phase and morphology of the products. But the XRD relative intensity of（001） surface of magnesium hydroxide declines, the specific surface area reduces apparently and the additive mass of lithium affects the heat loss rates of precipitations obviously. Quantum chemical calculations on the interactional systems of Mg（H2O）2＋6 and Li（H2O）＋4 were performed using B3LYP/6-311 G basis set. The results show that when the distance of Mg2＋ and Li＋ is 7-10 , the interaction energy is high and the trend of solvation is strong, which would make hydroxide ions easier to combine with hydrogen ions in ammonia precipitation process. And the absolute value of solvation free energy reduces significantly in MgCl2 solution（1 mol/L） containing lithium ion.
