Four vinyl polymer gels (VPGs) were synthesized by free radical polymerization of divinylbenzene, ethane‐1,2‐diyl dimethacrylate, and copolymerization of divinylbenzene with styrene, and ethane‐1,2‐diyl dimethacrylate with methyl methacrylate, as supports for palladium nanoparticles. VPGs obtained from divinylbenzene and from divinylbenzene with styrene had spherical shapes while those obtained from ethane‐1,2‐diyl dimethacrylate and from ethane‐1,2‐diyl dimethacrylate with methyl methacrylate did not have any specific shapes. Pd(OAc)2 was impregnated onto VPGs and reduced to form Pd0 nanoparticles within VPGs. The structures of Pd0‐loaded VPGs were analyzed by XRD, TEM, and nitrogen gas adsorption. Pd0‐loaded VPGs had nanocrystals of Pd0 within and on the surface of the polymeric supports. Pd0/VPGs efficiently catalyzed the oxidation/disproportionation of benzyl alcohol into benzaldehyde/toluene, where activity and selectivity between benzaldehyde and toluene varied, depending on the structure of VPG and the weight percentage loading of Pd0. The catalysts were stable and Pd leaching to liquid phase did not occur. The catalysts were separated and reused for five times without any significant decrease in the catalytic activity.
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