Hemishell Zeolites Synthesized by Asymmetric Modification as Biphasic Nanoreactors with Tunable Amphiphilicity for Catalysis of Cascade Reactions

It is strongly desired to design and synthesize amphiphilic nanoreactors with tunable compatibility, which are stable at the biphasic interface in both acidic and alkaline environments. Herein, a novel amphiphilic R1-ZSM-5-R2 nanoreactor with adjustable hydrophilic–lipophilic balance (solid) (HLB­(S)) values has been successfully synthesized by hydrophilic/lipophilic asymmetric modification of the surface of hemishell zeolites. The hemishell zeolites obtained by alkali etching have different surfaces for this asymmetric modification. Owing to the unique hemishell structures and asymmetric modification, the R1-ZSM-5-R2 nanoreactors with an optimized type and amount of modified organosilanes show excellent stability and emulsifying properties under extreme environments, which is important for cascade reactions in a biphasic system. The modified amino groups on the surface of the nanoreactors not only enhance the hydrophilicity of the hemishell zeolites and stabilize ultrasmall Pt nanoparticles (1.90 nm) but also used for the catalytic synthesis of trans-cinnamaldehyde. The Pt@R1-ZSM-5-R2 amphiphilic catalysts fabricated through a one-step reduction of Pt nanoparticles present outstanding performances in the biphasic cascade synthesis of cinnamic acid, achieving a very high turnover frequency (TOF) of 978 h–1. The TOF values of the catalysts correspond well to the HLB­(S) values of the R1-ZSM-5-R2 nanoreactors.