Microwave-assisted catalytic transfer hydrogenolysis of lignin-derived aromatic ethers over Ru/C

Cleavage of aromatic ether bonds through hydrogenolysis is one of the most promising routes for depolymerisation and transformation of lignin into value-added chemicals. Herein, we investigate the catalytic transfer hydrogenolysis (CTH) of benzyl phenyl ether (BPE), as a model molecule of alpha-O-4 lignin linkages, over commercial Ru/C under microwave irradiation using 2-propanol as H-donor. By tuning the reaction parameters, such as time, temperature and catalyst amount, BPE was fully converted, at 150 degrees C in 5 min of irradiation, with a related aromatics selectivity of 92%. Phenylethylphenyl ether (PPE), and diphenyl ether (DPE), as a models of beta-O-4 and 4-O-5 linkages, respectively, were also considered to this scope and under optimized reaction conditions, >99% and 72% conversion, respectively, were achieved with >89% aromatics selectivity. Remarkably, catalytic tests with moderate conversions clearly showed that the cleavage of etheric C-O bond was the primary step under CTH conditions, while the hydrogenations of the aromatic rings take place in a subsequent step. Overall, the screening of the reaction parameters was crucial to avoid the hydrogenation of aromatic rings. No less significant was the Ru/C stability, which has been recycled at least six times without any noticeable activity loss.

Automated summary

The catalytic transfer hydrogenolysis of aromatic ether bonds was successfully achieved under optimized reaction conditions, converting lignin into valuable chemicals. The reaction parameters were crucial to avoid the hydrogenation of the aromatic rings. The Ru/C catalyst demonstrated excellent stability, showing no noticeable activity loss even after six cycles of recycling.