Construction of a stable NiCo@ZrO2/N-doped biomass carbon composite with layer-by-layer embedding structure and strong interactions for efficient catalytic hydrogenolysis of 5-hydroxymethylfurfural

Catalytic transfer hydrogenolysis (CTH) of biomass-derived 5-hydroxymethylfurfural (HMF) by non-noble metal composites is a potential method for producing the liquid fuel 2,5-dimethylfuran (DMF). However, rigorous reaction conditions (≥ 240 °C; ≥ 6 h) lead to the deactivation of composite catalysts and limit their industrial application. Herein, a mechanical activation (MA)-enhanced dispersion and layer-by-layer imbedding strategy was created to construct an efficient and stable MA-NiCo@ZrO 2 /NBC composite for selective catalytic hydrogenolysis of HMF to produce DMF. The MA-NiCo@ZrO 2 /NBC composite with strong metal–metal and metal–support interactions exhibited outstanding catalytic performance for the conversion of HMF with formic acid as a hydrogen source, achieving a HMF conversion of 99.3% and a DMF yield of 96.7% at 200 °C for 2 h (96.7 times higher than those by the catalyst without MA treatment). Comparative investigations reveal that the formation of NiCo alloy and fast electron transfer of metal–acid bifunctional sites improved the preferential adsorption of C=O, and the formate intermediate promoting C–O hydrogenolysis also kept the furan ring intact. Moreover, MA-NiCo@ZrO 2 /NBC with stable structure maintained good catalytic activity after eight cycles. This study provides an attractive strategy for developing efficient and stable non-noble metal composites for catalytic upgrading of biomass-derived chemicals under mild conditions.