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C-lignin is a homo-biopolymer, being made up of caffeyl alcohol exclusively. There is significant interest in developing efficient and selective catalyst for depolymerization of C-lignin, as it represents an ideal feedstock for producing catechol derivatives. Here we report an atomically dispersed Ru catalyst, which can serve as an efficient catalyst for the hydrogenolysis of C-lignin via the cleavage of C−O bonds in benzodioxane linkages, giving catechols in high yields with TONs up to 345. A unique selectivity to propenylcatechol (77%) is obtained, which is otherwise hard to achieve, because this catalyst is capable of hydrogenolysis rather than hydrogenation. This catalyst also demonstrates good reusability in C-lignin depolymerization. Detailed investigations by model compounds concluded that the pathways involving dehydration and/or dehydrogenation reactions are incompatible routes; we deduced that caffeyl alcohol generated via concurrent C−O bonds cleavage of benzodioxane unit may act as an intermediate in the C-lignin hydrogenolysis. Current demonstration validates that atomically dispersed metals can not only catalyze small molecules reactions, but also drive the transformation of abundant and renewable biopolymer.

Selective hydrogenolysis of catechyl lignin into propenylcatechol over an atomically dispersed ruthenium catalyst