Adsorptive Separation Of Light Hydrocarbons And Catalysis Of CO₂ Cycloaddition Over Novel MOFs Or POP Materials

Efficient separation of light hydrocarbons and efficient conversion of CO₂ are greatly challenging.This work was mainly focused on the design and synthesis of novel MOFs or POP materials for the efficient separation performances of light hydrocarbons and CO₂ cycloaddition reaction.It was involved with the study of the synthesis of several MOFs and POP materials for efficient separation of light hydrocarbons and the preparation of high-metal-density MMPF materials for the high-efficient catalysis of the cycloaddition reaction of CO₂ with aziridines,which belongs to the interdisciplinary fields of chemical engineering,catalytic chemistry and material engineering.It is of great significance for the scientific research and practical applications.A series of Ni?BDC?_1-x?TMBDC?_x?DABCO?_0.5?x=0,0.2,0.45,0.71,1?were synethesized and their separation performance toward C₂H₆/C₂H₄ binary mixture was examined.Ni?BDC??DABCO?_0.5 was selected as a prototype host material and the TMBDC ligand was introduced into the framework through a mixed-ligand strategy,affording a series of Ni?BDC?_1-x?TMBDC?_x?DABCO?_0.5?x=0,0.2,0.45,0.71,1?.The highest C₂H₆ capacity of5.45 mmol/g and C₂H₄ capacity of 5.02 mmol/g were achieved on Ni?TMBDC??DABCO?_0.5,as well as C₂H₆/C₂H₄ selectivity of 1.945.The separation performance of C1/C2/C3 over an ultramicroporous material Ni?TMBDC??DABCO?_0.5 was investigated.Its adsorption capacity reached 2.93 mmol/g for C₂H₆ at 10 kPa and 3.37 mmol/g for C₃H₈ at 5 kPa.Its IAST selectivity for C2/C1 and C3/C1were 29 and 274,respectively,which were the higher than the most of the reported data.The molecular simulation revealed the C₂H₆ and C₃H₈ were preferentially adsorbed around the methyl groups and methylene groups,demonstrating the presence of large amount of methyl groups and methylene groups in the channels enhanced the adsorption and selectivity of C₂H₆and C₃H₈ on Ni?TMBDC??DABCO?_0.5.A novel strategy for room temperature synthesis of MIL-100?Fe?was proposed.RT-MIL-100?Fe?was successfully prepared at room temperature by using BQ as an accelerant and iron powder as metal source.The mechanism of oxidizing radicals promoting room temperature synthesis of MIL-100?Fe?was subsequently proposed.In addition,the C1/C2/C3 adsorption of the as-synthesized RT-MIL-100?Fe?was investigated.At 298 K and 1 bar,the adsorption capacity of C₂H₆ and C₃H₈ reached 2.22 mmol/g and 6.77 mmol/g on RT-MIL-100?Fe?,respectively.Fixed bed experiments confirmed that completely C1/C2/C3 ternary mixture was completely separated through the fixed-bed of RT-MIL-100?Fe?.A porous organic polymer,CPOP was successfully synthesized through“Click reaction”for the CH₄/C₂H₆/C₃H₈ separation.The CPOP showed high BET surface area of 1038 m²/g and excellent stability under acid/basic condition.Breakthrough experiment demonstrated complete separation of C1/C2/C3 mixture through the fixed-bed of CPOP with great recycliability.The molecular simulation showed that the CH₄,C₂H₆ and C₃H₈ molecules were preferentially adsorbed around the N atoms of the triazine ring,forming weak interaction with the N atoms.A novel metal-metalloporphyrin framework,MMPF-10 was synthesized and its catalytic performance in cycloaddition reactions between aziridines and CO₂ was explored.MMPF-10possessed an fmj topology with high density of Cu sites that oriented toward the channel.The MMPF-10 was used as a heterogeneous catalyst for CO₂ cycloaddition with aziridines and>99%yield of the 3-methyl-5-phenly-2-oxazolidinone was obtained at 100°C,2 MPa.