Controlling product selectivity by surface defects over MoOx-decorated Ni-based nanocatalysts for γ-valerolactone hydrogenolysis.

• MoO x -decorated Ni-based catalysts were fabricated via a single-source precursor route. • As-fabricated Ni-based catalyst was highly active for γ-valerolactone hydrogenolysis. • Surface defective MoO x species facilitated the activation of carbonyl group. • A cooperation between Ni0 species and surface defects contributed to high efficiency. Currently, highly efficient biomass upgrading over non-noble metal catalysts is of vital importance for reducing equipment and operation expenses in biorefinery industries. In this respect, the related heterogeneous catalysis demands the design and construction of mutual cooperative microstructure of catalysts to improve their catalytic performances. Here, an efficient catalytic process for selective hydrogenolysis of biomass-derived γ-valerolactone (GVL) to produce 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF) was developed by earth-abundant nickel-based catalysts, which were derived from a molybdate intercalated Ni-Al layered double hydroxide precursor. It was found that with the elevated reduction temperature, the amount of surface defective MoO x species (0 < x < 3) was gradually increased. Especially, as-fabricated Ni-MoO x /Al 2 O 3 catalyst obtained at the reduction temperature of 600 °C delivered a 94.0% combined yield of 1,4-PDO and 2-MTHF under mild reaction conditions. It was demonstrated that over the present Ni-MoO x /Al 2 O 3 catalyst system, surface defective MoO x species could greatly facilitate the adsorption and activation of carbonyl group in GVL and thus significantly promote the cleavage of C O bond and its adjacent C O bond. This finding opens a promising door to engineer surface defective structure of high-performance supported metal catalysts. [ABSTRACT FROM AUTHOR]