Gas phase synthesis and adsorption properties of a 3D ZIF-8 CNT composite

The metal organic framework structure ZIF-8 has been grown directly on vertically aligned carbon nano tubes (VACNT) by a solid vapour transformation of a ZnO@VACNT composite with gaseous 2-methylimidazole. The ZnO@VACNT composite was synthesised by atomic layer deposition (ALD) using diethylzinc and water as precursors resulting in a homogeneous distribution of crystalline ZnO particles with an average size of 13 nm within the 3D VACNT host structure. The ZnO@VACNT composite was transformed to ZIF-8 by reaction with 2-methyl-imidazole (Hmim) while maintaining the 3D VACNT structure employing a solid vapour transformation reaction. Reaction time and temperature were identified as key parameters to control the generated surface area and the degree of conversion of the nanoscaled ZnO particles. 80 °C and 72 h were found to be sufficient for a complete conversion while longer reaction times result in even higher surface areas of the formed ZIF-8@VACNT composite. Surface areas of up to 1569 m$^{2}$ g$^{-1}$ could be achieved. Temperatures below 80 °C led to an incomplete conversion even under longer reaction times of up to 6 weeks. Finally, the CO$_{2}$ adsorption properties of the ZIF-8@VACNT composite were evaluated. A composite with a 27 w% content of CNTs and a surface area of 1277 m$^{2}$ g$^{-1}$ shows an adsorption of 6.05 mmol g$^{-1}$ CO$_{2}$ at 30 bar. From the comparison with the pristine materials ZIF-8 and VACNT alone the observed overall CO$_{2}$ adsorption behaviour of the composite is a combination of the behaviour of the individual components, ZIF-8 and VACNTs. Namely the typical steep rise of the ZIF-8 in the low-pressure regime with a nearly linear steady progression in the medium pressure size regime, the latter typical for VACNTs, proves that the combination of both components leads to enhanced adsorption properties of the ZIF-8@VACNT composite compared to the sole components ZIF-8 and VACNTs