Magnetic Pt single and double core-shell structures for the catalytic selective hydrogenation of cinnmaladehyde

Abstract

This study reports the catalytic preparation, characterization, and evaluation of nanoscale coreshell structures with a gamma-Fe2O3 core covered by a SiO(2 )monoshell or by a SiO2@TiO2 multishell as a support for Pt nanoparticles (NPs) to synthesize active and operationally stable catalysts for selective liquid-phase cinnamaldehyde hydrogenation. The structures were designed with a magnetic core so they could be easily recovered from the catalytic bed by simple magnetization and with a SiO2 monoshell or a SiO2@TiO2 multishell to protect the magnetic core. At the same time, this study details the effect of the shell on the catalytic performance. Moreover, the effect of particle size on the selective production of cinnamyl alcohol was studied by preparing two families of catalysts with metal loadings of 1 wt% and 5 wt% Pt with respect to the coreshell. The particle size effect enabled the Fe2O3@SiO2-5%Pt system, with an average particle size of 5.6 nm, to reach 100% conversion of cinnamaldehyde at 300 min of reaction, producing cinnamyl alcohol with 90% selectivity; this result differed greatly from that of the Fe2O3@SiO2-1%Pt (d(Pt) =3.5 nm) system, which reached a maximum conversion at 600 min with 49 % selectivity for the product of interest. However, the Fe2O3@SiO2@TiO2-x%Pt systems showed lower levels of conversion and selectivity compared to those of the Fe2O3@SiO2-x%Pt catalysts, which is attributed to the fact that average metal particle sizes below 5.0 nm were obtained in both cases. After reduction in H Z at 773 K, the Fe2O3@SiO2@TiO2 1%Pt catalyst showed deactivation, reaching 10% conversion at 600 min of reaction and 60 % selectivity for the product of interest. However, the reduced Fe2O3@SiO2@TiO2-5%Pt system showed 98 % conversion with 95% selectivity for cinnamyl alcohol at 24 h of operation; the increase in selectivity is attributed to the combined effects of the increase in average particle size (similar to 7.5 nm) and the presence of strong metal-support interaction - SMSI - effects after reduction. Finally, the most selective systems were tested for operational stability, where the Fe2O3@SiO2@-5%Pt catalyst could be reused in three consecutive operating cycles while maintaining its activity and selectivity for cinnamyl alcohol - unlike the Fe2O3@SiO2@TiO2 5%Pt reduced system, which was deactivated after the third reaction cycle due to active phase leaching.