One-Pot Synthesis of Highly Active and Hydrothenmal Stable Pd@mHSiO2 Yolk–Shell-Structured Nanoparticles for High-Temperature Reactions in Hydrothermal Environments.

The facile synthesis of yolk–shell-structured nanoparticles (YSNPs) with mobile active metal cores and mesoporous inorganic–organic hybrid silica shells (mHSiO2) is important for their application. In this work, Pd@mHSiO2 YSNPs have been synthesized in aqueous solution at 95 °C by a one-pot method without the need for extensive purification and separation steps. The method is simple and facile, and ingeniously combines the controlled synthesis of Pd nanocubes, coating of mesoporous silica, and transition from core–shell-structured nanoparticles (CSNPs) to YSNPs. 29Si NMR spectra, FTIR spectra, and detailed control experiments have demonstrated that the incorporation of 1,2-bis(trimethoxysilyl)ethane (BTME) modifies the degree of condensation between an outer hybrid silica layer and an inner pure silica section, and that high temperature water is really responsible for dissolving the inner pure silica layer leading to a transition from CSNPs to YSNPs. The obtained Pd@mHSiO2 YSNPs are of controllable diameter, tunable shell thickness, high specific surface area, and uniform mesoporosity. Thermal stability tests have indicated that Pd@mHSiO2 YSNPs are remarkably stable at high temperatures up to 650 °C. Importantly, Pd@mHSiO2 YSNPs exhibit much higher catalytic activity and hydrothermal stability than Pd@mSiO2 CSNPs or Pd/mHSiO2 NSs in the conversion of levulinic acid (LA) into γ-valerolactone (GVL), because the hollow voids provide low mass-transfer resistance and improve the accessibility of the catalytic sites, and the incorporation of organic groups enhances the hydrothermal stability of the outer shell.