Sulfonic acid-functionalized core-shell Fe_3O_4@carbon microspheres as magnetically recyclable solid acid catalysts

Green and recyclable solid acid catalysts are in urgent demand as a substitute for conventional liquid mineral acids.In this work,a series of novel sulfonic acid-functionalized core-shell Fe_3 O_4@carbon microspheres(Fe_3 O_4@C-SO_3 H) have been designed and synthesized as an efficient and recyclable heterogeneous acid catalyst.For the synthesis,core-shell Fe_3 O_4@RF(resorcinol-formaldehyde) microspheres with tunable shell thickness were achieved by interfacial polymerization on magnetic Fe_3 O_4 microspheres.After high-temperature carbonization,the microspheres were eventually treated by surface sulfonation,re sulting in Fe_3 O_4@C-x-SO_3 H(x stands for carbonization temperature) microspheres with abundant surface SO_3 H groups.The obtained microspheres possess uniform core-shell structure,partially-graphitized carbon skeletons,superparamagnetic property,high magnetization saturation value of 10.6 emu/g,and rich SO_3 H groups.The surface acid amounts can be adju sted in the range of 0.59-1.04 mmol/g via sulfonation treatment of carbon shells with different graphitization degrees.The magnetic Fe_3 O_4@C-x-SO_3 H microspheres were utilized as a solid acid catalyst for the acetalization reaction between benzaldehyde and ethylene glycol,demonstrating high selectivity(97%) to benzaldehyde ethylene glycol acetal.More importantly,by applying an external magnetic field,the catalysts can be easily separated from the heterogeneous reaction solutions,which later show well preserved catalytic activity even after 9 cycles,revealing good recyclability and high stability.