Selective C₃-C₄ Keto-Alcohol Production from Cellulose Hydrogenolysis over Ni-WOx/C Catalysts

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Keto-alcohols, which are traditionally produced from fossil resources with multisteps, are considered as important intermediates for diversified high-value-added fine chemical synthesis due to their involved carbonyl and hydroxyl groups. Herein, direct cellulose hydrogenolysis to C 3 -C 4 keto-alcohol products (hydroxyacetone and 1(3)-hydroxy-2-butanone) was achieved over Ni-WO x /C catalysts with an W/Ni atom ratio of 1.0–5.0. The keto-alcohol yield was proposed to strongly depend on the W/Ni ratio and the catalyst annealing temperature. The highest keto-alcohol yield of 63% was obtained at the optimal balance of basic/acidic WO x species and metallic Ni. The introduction of Ni facilitated the formation of the basic W 5+ sites, which enhanced the formation of basic sites at the Ni-WO x interface. The synergistic effect between the basic W 5+ and acidic oxygen vacancy (Vö) could activate the target C–O/C═O bonds, promoting the isomerization of glucose and C 3 -C 4 aldehyde intermediates with the assistance of the interfacial Ni. The cooperative adsorption of the −OH and −C═O groups at the Ni-O-W-Vö interface stabilized the adjacent ketone and hydroxyl groups and kept the other hydroxyl groups for hydrogenolysis, obtaining the final C 3 -C 4 keto-alcohols. This work expanded the application of cellulosic biomass, enabling the green and sustainable synthesis of the high-value C 3 -C 4 keto-alcohol products using lignocellulosic biomass as a raw material.