Synthesis of ZIF-11 Membranes: The Influence of Preparation Technique and Support Type

Due to its structural features, ZIF-11 is one of the most interesting materials for gas separation applications. Herein, we report a systematic study on the synthesis of ZIF-11 as a supported membrane. For this, we adapted optimized conditions for the ZIF-11 powder synthesis, identified in our previous works, to form ZIF layers on symmetric and asymmetric stainless-steel and asymmetric α-Al₂O₃ supports. Different techniques were investigated for the challenging layer formation, namely, in situ crystallization (ISC), multiple in situ crystallization (MISC), and the seeding and secondary growth (SSG) method. It was possible to deposit ZIF-11 on different supports by ISC and MISC, although it was difficult to obtain complete layers. SSG, in turn, was more effective in forming dense and well-intergrown ZIF-11 layers. This agrees well with the generally accepted fact that seeding considerably facilitates layer formation. Systematic studies of both individual steps of SSG (seeding and secondary growth) led to a basic understanding of layer formation of ZIF-11 on the different supports. The best membranes prepared by rub seeding and secondary growth achieved Knudsen selectivity. Improved gas separation performance is expected if the formation of defects can be avoided.