Selective Hydrodeoxygenation of Lignin‐Derived Vanillin via Hetero‐Structured High‐Entropy Alloy/Oxide Catalysts

The chemoselective hydrodeoxygenation of natural lignocellulosic materials plays a crucial role in converting biomass into value‐added chemicals. Yet their complex molecular structures often require multiple active sites synergy for effective activation and achieving high chemoselectivity. Herein, it is reported that a high‐entropy alloy (HEA) on high‐entropy oxide (HEO) hetero‐structured catalyst for highly active, chemoselective, and robust vanillin hydrodeoxygenation. The heterogenous HEA/HEO catalysts were prepared by thermal reduction of senary HEOs (NiZnCuFeAlZrO x ), where exsolvable metals (e.g., Ni, Zn, Cu) in situ emerged and formed randomly dispersed HEA nanoparticles anchoring on the HEO matrix. This catalyst exhibits excellent catalytic performance: 100% conversion of vanillin and 95% selectivity toward high‐value 2‐methyl‐4 methoxy phenol at low temperature of 120 °C, which were attributed to the synergistic effect among HEO matrix (with abundant oxygen vacancies), anchored HEA nanoparticles (having excellent hydrogenolysis capability), and their intimate hetero‐interfaces (showing strong electron transferring effect). Therefore, our work reported the successful construction of HEA/HEO heterogeneous catalysts and their superior multifunctionality in biomass conversion, which could shed light on catalyst design for many important reactions that are complex and require multifunctional active sites.