Polar alcohol guest molecules regulate the stacking modes of 2-D MOF nanosheets.

The modulation of two-dimensional metal-organic framework (2-D MOF) nanosheet stacking is an effective means to improve the properties and promote the application of nanosheets in various fields. Here, we employed a series of alcohol guest molecules (MeOH, EtOH and PrOH) to modulate Zr-BTB (BTB = benzene-1,3,5-tribenzoate) nanosheets and to generate untwisted stacking. The distribution of stacking angles was statistically analyzed from high-angle annular dark-field (HAADF) and fast Fourier transform (FFT) images. The ratios of untwisted stacking were calculated, such as 77.01% untwisted stacking for MeOH, 83.45% for EtOH, and 85.61% for PrOH. The obtained untwisted Zr-BTB showed good separation abilities for different substituted benzene isomers, superior selectivity and excellent column stability and reusability. Control experiments of 2-D Zr-TCA (TCA = 4,4',4''-tricarboxytriphenylamine) and Zr-TATB (TATB = 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzoic acid) nanosheets with similar pore sizes and stronger polarity regulated by the alcohol guests exhibited moderate separation performance. The electron microscopy images revealed that polar alcohol regulation dominantly generated the twisted stacking of Zr-TCA and Zr-TATB with various Moiré patterns. Polar guest molecules, such as alcohols, provide strong host-guest interactions during the regulation of MOF nanosheet stacking, providing an opportunity to design new porous Moiré materials with application prospects.