Synthesis of 1‐MP Over Modified ZIF‐94 Catalysts

This article reports the modification of the hydrophilic aldehyde groups of ZIF‐94 into new hydrophobic functional groups through a reduction reaction (yielding ZIF‐94/Redu) and an imine condensation reaction (yielding ZIF‐94/Cond). The basic sites of ZIF‐94, ZIF‐94/Redu, and ZIF‐94/Cond were investigated, and for the first time, the materials were subsequently used as catalysts for the reaction between propylene oxide (PO) and methanol (MeOH) to synthesize 1‐methoxy‐2‐propanol (1‐MP). The modification of ZIF‐94 using different agents was comprehensively evaluated by XRD, FT‐IR, SEM, TEM, DTA/TGA, N 2 adsorption–desorption, CO 2 ‐TPD, and GC‐MS analyses. The results showed that the modified materials exhibited decreased crystallinity and specific surface area but enhanced hydrophobicity, thermal stability, and average mesopore size, resulting in pronounced changes in catalytic activity for the PO‐MeOH reaction. The results demonstrate that basic sites play a very important role, while the hydrophobicity of the catalyst can support enhanced PO conversion and 1‐MP selectivity. Under suitable conditions, the ZIF‐94/Cond catalyst afforded complete PO conversion and a 1‐MP selectivity of 90.79% after 7 h of reaction at 120°C.