Efficient selective hydrogenolysis of biomass-derived furfuryl alcohol to 1,5-pentanediol over rod-like La2O2CO3-supported Ni nanoparticle catalyst

The effects of catalyst preparation and reaction conditions, feedstocks, and catalyst reusability were investigated. • The morphologies of catalyst evolution from sheet-like structures to nanorods were controlled by hydrothermal treatment. • Morphology control is associated with metal-support interactions and promotes selective ring opening. • Rod-like Ni@La 2 O 2 CO 3 delivers a remarkable 76.9 ± 0.3% yield of 1,5-pentanediol from furfuryl alcohol. • DFT calculations indicate that the catalyst favors the 1,5-PeD pathway with a low barrier of 1.46 eV and an exothermicity of –0.53 eV. The selective hydrogenolysis of biomass-derived furfuryl alcohol (FA) to 1,5-pentanediol (1,5-PeD) represents a sustainable alternative to petrochemical routes, yet achieving high selectivity over non-noble metal catalysts remains a significant challenge due to competing side reactions. Herein, we report an efficient catalyst featuring Ni nanoparticles supported on rod-like lanthanum oxycarbonate (Ni@La 2 O 2 CO 3 ). Under optimized preparation and reaction conditions, the catalyst achieves complete FA conversion and a remarkable 1,5-PeD yield of 76.9 ± 0.3%, with a moderately high space-time yield (STY) of 1.13 ± 0.01 g 1,5-PeD ·g cat –1 ·h –1 . The morphological evolution from sheet-like structures to nanorods via controlled hydrothermal treatment significantly correlates with the interfacial synergy between Ni and La 2 O 2 CO 3 and boosts the 1,5-PeD yield. Density functional theory (DFT) calculations further elucidate the mechanistic origin of the high regioselectivity, identifying an interface that induces electron accumulation on the Ni active sites. This electronic modulation significantly lowers the activation barrier for the C–O bond cleavage of the tetrahydrofurfuryl alcohol intermediate to 1.46 eV for the 1,5-PeD pathway, compared to 1.72 eV for the 1,2-PeD route. This work provides an efficient strategy for the rational design of morphology-controlled non-noble catalysts for the high-value valorization of biomass. Download: Download high-res image (185KB) Download: Download full-size image