Tuning Product Selectivity in Levulinic Acid Hydrogenation via Non-Noble Nanocatalysts Derived from Metal–Organic Frameworks

Catalytic conversion of renewable lignocellulosic biomass into fine chemicals is an effective approach to realizing sustainable development, among which the development of nonprecious-metal-based catalysts to one-pot conversion of levulinic acid (LA) to 1,4-pentanediol (1,4-PDO) under mild conditions remains a challenging and important target. Here, we report a series of bimetallic CoNi-ZIF-derived nanocatalysts for LA hydrogenation; all of the prepared catalysts exhibited complete LA conversion, while the product selectivity varied greatly due to the differences in hydrogenation ability and acidic sites. The pyrolysis conditions had great influence on both catalyst composition and product selectivity. CoNiOx@quasi-ZIF obtained by partial pyrolysis CoNi-ZIF lacked sufficient hydrogenation sites, leading to γ-valerolactone (GVL) as the dominant product. In contrast, the complete pyrolysis catalyst CoNi@NC with N-doped carbon-confined CoNi nanoalloy had abundant hydrogenation sites and acid sites, resulting in good 1,4-PDO yield of 74.6% in just 4 h of reaction time. This work emphasized the synergy between hydrogenation sites and acidic sites in LA one-pot conversion and offered a promising nanocatalyst for sustainable chemical synthesis.