Investigating the Long-Term Kinetics of Pd Nanoparticles Prepared from Microemulsions and the Lindlar Catalyst for Selective Hydrogenation of 3-Hexyn-1-ol

Abstract

The effect of non-saturated corner and edge sites of Pd particles on the long-term selectivity of cis-3-hexen-1-ol in the hydrogenation of 3-hexyn-1-ol was studied in this work. Non-supported Pd agglomerates were synthesized through the microemulsion synthesis route and used at nalkynol/APd ratios between 0.08 and 21 mol/m2 for the catalytic conversion of 3-hexyn-1-ol for 20 h. The selectivity of the cis-hexenol product increased by reducing the quantity of Pd catalytic sites (increasing the nalkynol/APd ratio) without introducing any modifier or doping agent to poison the nonselective sites. Then, Pd aggregates with fused primary particles and, thus, fewer corner and edge sites were produced through thermal sintering of the agglomerates at 473–723 K. By comparing the catalytic performance of the agglomerates and aggregates, it was observed that at a rather similar kinetic behavior (99.99% conversion and 85–89% selectivity to cis-hexenol), the sintered aggregates could stay selective despite a catalytic surface area about seven times larger. This emphasizes the role of low-coordinated edge and corner sites on the final selectivity of the cis product and demonstrates that thermal sintering allows the number of non-selective sites to be reduced without any need for toxic or organic doping agents or modifiers.

Keywords

• catalytic hydrogenation
• Lindlar replacement
• Pd nanoparticles
• structure–activity relationship
• microemulsion