Layer-by-layer assembly of zeolite crystals on glass with polyelectrolytes as ionic linkers

ZSM-5 crystals and glass plates tethered with trimethylpropylammonium iodide and sodium butyrate, respectively, (denoted as Z(+), Z(-), G(+), and G(-), respectively) were prepared. Treatment of G(-) with Z(+) suspended in ethanol results in monolayer assembly of Z(+) on G(-) (G(-)/Z(+)) with high surface coverage. The zeolite crystals have a strong tendency to closely pack and align with the b-axis normal to the glass plate, despite large positive zeta potentials. Subsequent treatment of G-/Z+ with Z- leads to second-layer assembly of Z(-) on G(-)/Z(+) (G(-)/Z(+)/Z(-)), but with rather poor coverage. Sequential treatment of G(+) with poly(sodium 4-styrenesulfonate) (Na+PSS-), poly(diallyidimethylammonium chloride) (PDDA(+)Cl(-)), and Na+PSS- followed by Z(+) yields glass plates assembled with monolayers of Z(+) with very high surface coverage through the composite polyelectrolyte linkers (G(+)/PSS-/PDDA(+)/PSS-/Z(+)). The zeolite crystals also have a strong tendency to closely pack and align with the b-axis perpendicular to the substrate plane. The binding strength between the zeolite crystals and glass plates is much higher in G(+)/PSS-/PDDA(+)/PSS-/Z(+) than in G(-)/Z(+). Repetition of the sequential PSS-/PDDA+/PSS-/Z+ layering for five cycles yields glass plates assembled with pentalayers of ZSM-5 crystals [G(+)/(PSS-/PDDA(+)/PSS-/Z(+))(5)]. The observed degrees of coverage and alignment of zeolite crystals in each layer were very high up to the third layers despite the nonuniformity of the sizes and shapes of the zeolite crystals used in this study. This report thus demonstrates the feasibility of layer-by-layer assembly of micrometer-sized zeolite crystals on glass through electrostatic interaction between surface-bound, full-fledged ionic centers, especially by use of polyelectrolyes as the linkers.