Isolated Nano-Island Catalysts Enable Efficient Double-Bond Migration over Pd Nanoparticles.

Lu, Bing; Liang, Shipan; Liu, Yanling; Liu, Wencong; Liu, Ting; Zhang, Liwei; Chen, Zhengyang; Ying, Sibin et al. · ACS Nano · 2025

basic_science · Level V

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Abstract

Nanoparticles (NPs) play a key role in heterogeneous catalysis due to their unique nanoscale effects, but their thermodynamic instability makes stabilizing small metal species challenging. Herein, we develop a series of Pd/xCeO<sub>2</sub>/SiO<sub>2</sub> catalysts with a nanoisland architecture that enables precise control over Pd particle size and electronic properties via a confinement effect. CeO<sub>2</sub> nanoparticles were first dispersed on a SiO<sub>2</sub> support, followed by selective Pd deposition on the CeO<sub>2</sub> surface through strong metal-support interactions and electron transfer between Pd and reducible CeO<sub>2</sub>. The resulting in situ-formed nanoisland structure enhances catalytic performance through optimized Pd-CeO<sub>2</sub> synergy. In the double-bond migration (DBM) of 2-pentylidene cyclopentanone, a key step in fragrance synthesis, the Pd/7%CeO<sub>2</sub>/SiO<sub>2</sub> catalyst achieved 90% isomerization selectivity at full conversion and a TOF of 26,000 h<sup>-1</sup>, 3-8 times higher than single-support catalysts. This catalyst has been successfully scaled up for the kiloton-scale annual production of methyl dihydrojasmonate, demonstrating the industrial relevance of this nanostructuring strategy.