Design Porous Materials With High Gas Separation Properties Based On Insertion/Substitution

In recent years,porous materials have attracted much attentions because of their potential applications in gas storage,separation and catalysis.In this dissertation,we designed a series of novel porous materials by means of insertion and substitution,using grand canonical Monte Carlo?GCMC?and ab initio methods to make an in-depth research on the properties of gas adsorption and separation of the porous materials from different insights,which can provide the reference for the relevant experimental studies.The specific research contents are as follows:1.To explore the adsorption and separation properties of CO2 in a novel material consisting of a series of polyoxometalates?POMs?impregnated within supramolecular porous catenane?shorted as SPC?,grand canonical Monte Carlo?GCMC?simulations and ab initio calculations were employed.GCMC simulations showed this impregnation can enhance CO2/CH₄?or CO2/N2?selectivity almost 30 times compared to the bare SPC due to the strong interaction of CO2 with the nPOMs@SPC structures.And,the loading of CO2 inhibites the adsorption of CH₄?or N2?as CO2 occupying the preferred adsorption sites.Furthermore,the effect of number,mass,and volume of POMs inserted in SPC on CO2/CH₄?or CO2/N2?selectivity over large pressure range was investigated in detail.Additionally,the accurate ab initio calculations further confirmed our GCMC simulations.As a result,the proposed nPOMs@SPC structures are promising candidates for CO2/N2 and CO2/CH₄ separations.2.A series of novel material MOFs ?-? by substituting different ligands to improve gas?CO2,CH₄,CO and H₂?adsorption and separation properties were designed.GCMC simulation was used to predit the adsorption of CO2,CH₄,CO,H₂ and the selectivities of CO2/H₂,CO/H₂ and CH₄/H₂.The results showed H₂ prompt the uptake of CO2,while CO2 almost didn't affect the adsorption of H₂,meaning the designed MOFs could be good candidates for separating CO2 and H₂.Moreover,although H₂ has little effect on CO and CH₄,our designed material adsorbed few H₂ which means they could be used to separate CO,CH₄ from H₂ as well.This study also provides a certain direction and research reference for experiments.