Preparation of Zeolitic Imidazolate Framework-8-Based Nanofiber Composites for Carbon Dioxide Adsorption.

In this study, polyacrylonitrile (PAN)-based activated nanofiber composites, which were embedded inside zeolitic imidazolate framework-8 (ZIF-8) crystals or ZIF-8-derived carbons (ZDC-850), were fabricated using an electrospinning process, to serve as CO2 adsorbents. The adsorbents were characterized using various techniques. The degree of crystallinity of ZDC-850 totally changed compared to that of ZIF-8. For nanofiber composites, the timing of the ligand decomposition of ZIF-8 significantly affected the material properties. The Zn metals in the ZIF-8/PAN or ZDC-850/PAN could be embedded and protected by the PAN fibers from excess volatilization in the following treatments: ZIF-8 had significant pore volumes in the range of 0.9−1.3 nm, but ZDC-850 and ZIF-8/PAN exhibited a distinct peak at approximately 0.5 nm. The CO2 adsorption capacities at 25 °C and 1 atm followed the order: ZIF-8/PAN (4.20 mmol/g) > ZDC-850 (3.50 mmol/g) > ZDC-850/PAN (3.38 mmol/g) > PAN (2.91 mmol/g) > ZIF-8 (0.88 mmol/g). The slope in the log−linear plot of isosteric heat of adsorption was highly associated with CO2 adsorption performance. Under 1 atm at 25 °C, for Zn metal active sites inside the pores, the pores at approximately 0.5 nm and in C-N (amines) groups could promote CO2 adsorption. At low CO2 pressures, for a good CO2 adsorbent, the carbon content in the adsorbent should be higher than a threshold value. Under this condition, the percentage of ultra-micropore and micropore volumes, as well as the functional groups, such as the quaternary or protonated N (amines), N=C (imines or pyridine-type N), C-OH, and -COOH groups, should be considered as significant factors for CO2 adsorption.