Herein, a catalytic reductive fractionation of lignocellulose is presented using a heterogeneous cobalt catalyst and formic acid or formate as a hydrogen donor. The catalytic reductive fractionation of untreated birch wood yields monophenolic compounds in up to 34 wt % yield of total lignin, which corresponds to 76 % of the theoretical maximum yield. Model compound studies revealed that the main role of the cobalt catalyst is to stabilize the reactive intermediates formed during the organosolv pulping by transfer hydrogenation and hydrogenolysis reactions. Additionally, the cobalt catalyst is responsible for depolymerization reactions of lignin fragments through transfer hydrogenolysis reactions, which target the β‐O‐4′ bond. The catalyst could be recycled three times with only negligible decrease in efficiency, showing the robustness of the system.
The catalytic properties of three types of mesoporous silica SBA-15 (rope, rod and fiber), with 9.2 nm or 12.1 nm large mesopores, were examined with respect to their morphology and pore size. Commercially available Amberlyst-15 and the small pore sized MCM-41 were used for comparison. The catalysts were prepared by functionalization of the silica supports with propyl sulfonic acid (Pr-SO3H) using post-synthesis grafting with 3-mercaptopropyltrimethoxysilane as a propyl-thiol precursor. All materials remained in a well-ordered hexagonal mesoporous structure after Pr-SO3H functionalization. The performance of the Pr-SO3H-functionalized mesoporous silicas was evaluated in terms of their catalytic activity in the esterification of oleic acid with short (methanol) and long (glycerol) chain alcohols, i.e. to test the effect of the pore size on the substrate conversion and product yield. The synthesized catalysts were highly active and the product composition could be tuned by selective choice of the mesopore size. The Pr-SO3H-functionalized rope-shaped SBA-15 gave the highest catalytic activity (in terms of the highest methyl oleate and triglyceride yields and oleic acid conversion level), which was higher than that obtained with the commercial Amberlyst-15 catalyst. A high acid amount, large specific surface area and a suitable pore size are the likely reasons for the high yield gained by Pr-SO3H-functionalized rope-shaped SBA-15 silica.
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