High quality pure-silica MFI-type zeolite membranes are successfully prepared by simply controlling the amount of structure directing agent (SDA), i.e., tetrapropylammonium (TPA⁺) in the synthesis solution for seeded growth. The effects of several synthesis parameters such as alkalinity (OH⁻/Si), TPA⁺ concentration (TPA⁺/Si), and crystallization time on the membrane pervaporation performance are investigated in detail. The synthesized MFI-type zeolite membranes are thoroughly characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, the water contact angle test, X-ray diffraction (XRD), the pervaporation test and gas permeation. The membrane microstructure is very sensitive to the TPA⁺/Si ratio of the synthesis solution. At a high TPA⁺/Si ratio (typically 0.17), parasitic twin crystals are intergrown in the zeolite layer, thus resulting in the formation of membrane defects during SDA removal treatment (calcination at 500 °C). When the membrane is prepared with a low TPA⁺/Si ratio (≤0.05), the appearance of twin crystals can be significantly suppressed and the synthesized dense MFI-type zeolite membranes exhibit pervaporation separation factors higher than 85 for 5 wt% ethanol–water mixtures at 60 °C. We demonstrate for the first time that controlling the SDA concentration in the precursor solution is beneficial to the elimination of membrane microstructural defects, showing a pathway to high quality MFI-type zeolite membranes.

Highly b-oriented MFI films are synthesized by simply controlling TPA⁺ concentration of the secondary synthesis solution to suppress the formation of a-oriented crystals. A formation mechanism is discussed for the films and also in the context of general MFI nucleation and crystallization.

A new route to the synthesis of highly b-oriented zeolite MFI films is demonstrated for the first time using ammonium salts as crystallization-mediating agents in secondary growth. The ammonium salts tailor the crystallization process and silicate–NH₄ ⁺ interactions dominate over TPA–NH₄ ⁺ interactions so that nucleation was effectively suppressed during secondary growth.