In situ construction of 3D NiMo bimetallic catalysts anchored on dendritic mesoporous silica for the upgrading of biomass derivatives

Reasonable construction of bi-function catalysts with well dispersed hydrogenation active sites and acidic sites are crucial for the hydrodeoxygenation (HDO) of biomass-derived compounds but still a huge challenge. Herein, a 3D Mo functionalized Ni-based bimetallic embedded catalyst with fine metal nanoparticles size (<6 nm) was prepared for the first time using dendritic mesoporous silica as a sacrificial template by one-pot hydrothermal synthesis and adopted in the HDO process of vanillin (VAN) upgrade to 2-methoxy-4-methylphenol (MMP). The characterization results illustrated that Mo species regulated the acidity of the catalyst and promoted the formation of Ni-Mo alloy sites. Density functional theory (DFT) calculations further unveiled that Ni-Mo alloy sites promoted the activation and dissociation of CO bond in VAN, enhanced the ability of protonation hydrogenolysis. Benefitting from the synergistic effect of the highly uniformly dispersed hydrogenation metal sites and acidic sites, nearly 100% yield of MMP could obtained over the designed catalyst under mild conditions (130 °C, 1.5 MPa H2, 3 h, 10 wt% catalyst dosage). Additionally, the NiMo0.1@MSN catalyst displayed robust activity for no less than 8 recycles and excellent universality for the HDO of a variety of lignin derivatives and biomass platform molecules, which provide a feasible strategy for the construction of 3D confined catalysts for the high-efficiency HDO of biomass derivatives.