Al-Doped Core-Shell-Structured Ni@Mesoporous Silica for Highly Selective Hydrodeoxygenation of Lignin-Derived Aldehydes.

Selective deoxygenation of chemicals using non-noble metal-based catalysts poses a significant challenge toward upgrading biomass-derived oxygenates into advanced fuels and fine chemicals. Herein, we report a bifunctional core-shell catalyst (Ni@Al-mSiO) consisting of Ni nanoparticles closely encapsulated by the Al-doped mesoporous silica shell that achieves 100% vanillin conversion and >99% yield of 2-methoxy-4-methylphenol under 1 MPa H at 130 °C in water. Due to the unique mesoporous core-shell structure, no significant decrease in catalytic activity was observed after 10 recycles. Furthermore, incorporating Al atoms into the silica shell significantly increased the number of acidic sites. Density functional theory calculations reveal the reaction pathway of the vanillin hydrodeoxygenation process and uncover the intrinsic influence of the Al sites. This work not only provides an efficient and cost-effective bifunctional hydrodeoxygenation catalyst but also offers a new synthetic protocol to rationally design promising non-noble metal catalysts for biomass valorization or other widespread applications.