The hydrogenation of glucose to sorbitol using Raney-Ni is a well-established process in industry, but it faces challenges such as high mannitol content, nickel leaching, and catalyst pyrophoricity. Here, Ni6Fe1/Al2O3 nanoflower with high sorbitol selectivity and stability was synthesized from NixFey/Al-LDH precursors, where the distribution of iron in the alloy phase and support can be well-regulated. XANES and FT-EXAFS spectra verified the presence of Fe in the catalyst as NiFe alloy and FeOx. Multiple evidences unveiled that the NiFe alloy phase significantly improving the yield of sorbitol and the iron oxide species can regulate the acidity of the support, thus effectively reducing the byproduct mannitol. Delightfully, the optimal Ni6Fe1/Al2O3 catalyst achieved a sorbitol yield of 99% and a mannitol yield of 0.45%, showing a significant advantage over Ni/Al2O3 (77% and 1.3%) and Raney-Ni (57% and 1.3%) catalysts. Theoretical calculations indicate that the NiFe alloy surface is more conducive to glucose adsorption and sorbitol desorption, and the intrinsic high activity of NiFe alloy phase is due to the downshift of d-band center, which facilitates H* dissociation from the anti-bonding orbital. This study provides significant insights for designing catalysts with high activity and selectivity in converting lignocellulosic biomass.

• •
  High active Ni6Fe1/Al2O3 was synthesized by reducing NixFey/Al-LDH precursors.
• •
  The Ni-Fe alloy greatly improves the hydrogenation activity of glucose.
• •
  The doping of iron in NiAl-LDH obviously reduces the amount and strength of acid.
• •
  The Ni6Fe1/Al2O3 shows high sorbitol selectivity and low mannitol yield.
• •
  The lower d-band center facilitates H* dissociation from the anti-bonding orbital.