Benedetti Francesco M, De Angelis Maria Grazia, Esposti Micaela Degli, Fabbri Paola, Masili Alice, Orsini Alessandro, Pettinau Alberto
Department of Civil, Chemical, Environmental and Materials Engineering, University of Bologna, 40131 Bologna, Italy.
Present address: Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Membranes (Basel). 2020 Mar 27;10(4):56. doi: 10.3390/membranes10040056.
In this study, we prepared and characterized composite films formed by amorphous poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and particles of the size-selective Zeolitic Imidazolate Framework 8 (ZIF-8). The aim was to increase the permselectivity properties of pure PPO using readily available materials to enable the possibility to scale-up the technology developed in this work. The preparation protocol established allowed robust membranes with filler loadings as high as 45 wt% to be obtained. The thermal, morphological, and structural properties of the membranes were analyzed via DSC, SEM, TGA, and densitometry. The gas permeability and diffusivity of He, CO, CH, and N were measured at 35, 50, and 65 °C. The inclusion of ZIF-8 led to a remarkable increase of the gas permeability for all gases, and to a significant decrease of the activation energy of diffusion and permeation. The permeability increased up to +800% at 45 wt% of filler, reaching values of 621 Barrer for He and 449 for CO at 35 °C. The ideal size selectivity of the PPO membrane also increased, albeit to a lower extent, and the maximum was reached at a filler loading of 35 wt% (1.5 for He/CO, 18 for CO/N, 17 for CO/CH, 27 for He/N, and 24 for He/CH). The density of the composite materials followed an additive behavior based on the pure values of PPO and ZIF-8, which indicates good adhesion between the two phases. The permeability and He/CO selectivity increased with temperature, which indicates that applications at higher temperatures than those inspected should be encouraged.
在本研究中,我们制备并表征了由非晶态聚(2,6-二甲基-1,4-苯醚)(PPO)和尺寸选择性的沸石咪唑酯骨架8(ZIF-8)颗粒形成的复合膜。目的是使用易得的材料提高纯PPO的渗透选择性,以便能够扩大本工作中开发的技术规模。所建立的制备方案能够得到填料含量高达45 wt%的坚固膜。通过差示扫描量热法(DSC)、扫描电子显微镜(SEM)、热重分析(TGA)和密度测定法对膜的热性能、形态和结构性能进行了分析。在35、50和65℃下测量了He、CO、CH和N的气体渗透率和扩散率。ZIF-8的加入导致所有气体的气体渗透率显著增加,扩散和渗透的活化能显著降低。在填料含量为45 wt%时,渗透率提高了800%,在35℃下He的渗透率达到621 Barrer,CO的渗透率达到449 Barrer。PPO膜的理想尺寸选择性也有所提高,尽管程度较低,在填料含量为35 wt%时达到最大值(He/CO为1.5,CO/N为18,CO/CH为17,He/N为27,He/CH为24)。复合材料的密度基于PPO和ZIF-8的纯值呈现加和行为,这表明两相之间具有良好的附着力。渗透率和He/CO选择性随温度升高而增加,这表明应鼓励在比所研究温度更高的温度下应用。