Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb2O5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7–C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb2O5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic–OH bonds in phenolics is significantly reduced upon adsorption on Nb2O5, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.

Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes.

The efficient utilization of lignocellulosic biomass has tremendous potential to reduce the excessive dependence on fossil fuels. Here, we provide an overview on the recent achievements in the catalytic production of value-added chemicals and fuels. When targeting chemicals, a key objective is to maximize the product selectivity to favor the subsequent separation. This can be achieved through the design of catalysts and optimization of catalytic systems based on the deep understanding of the catalytic mechanism. For production of fuels, attention should be paid to the establishment of an energy-efficient process for high-quality fuels. This can be realized through the design of C-C coupling reactions and the development of multifunctional catalysts to minimize the reaction steps from lignocellulose to fuels. In addition, the full utilization of lignocellulose into biofuels and chemicals in a single process is separately introduced. Finally, several personal perspectives on the opportunities and challenges within this promising field are discussed.

Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO(x)-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90% throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbO(x) species play the key role in C-O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbO(x) species help to cleave the C-O bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions.

No abstract