Fractionation of Lignocellulosic Biomass over Core-Shell Ni@Al2 O3 Catalysts with Formic Acid as a Cocatalyst and Hydrogen Source.

Highly dispersed, core-shell Ni@Al2 O3 on activated carbon (AC) catalysts were prepared to develop an effective, external-hydrogen-free fractionation process for various types of lignocellulosic biomass. In a mixture of formic acid, ethanol, and water at 190 °C, the conversion of oak wood produced 23.4 C% lignin-derived phenolic monomers (LDPMs) and highly delignified pulp-rich solid. At an early stage, formic acid acted as a cocatalyst to enhance the delignification by solvolysis, and at a later stage, it acted as a hydrogen source to stabilize the phenolic monomers by hydrodeoxygenation and hydrogenation. Based on the positive correlation between spillover hydrogen on the catalysts and LDPM yields, a new suite of catalyst design criteria was proposed to develop highly active, non-noble-metal based catalysts for realizing economically viable biorefineries. Enzymatic saccharification of the pulp-rich solid indicated that the pulp-rich solid is an excellent source of fermentable sugars.