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Abstract

The conversion of lignin, the most recalcitrant of the biopolymers, is necessary for a carbon-efficient utilization of lignocellulosic materials. In this context, hydrogenolysis of lignin is a process receiving increasing attention. In this report, the solvent effects on the hydrogenolysis of diphenyl ether and lignin with Raney Ni are addressed. The Lewis basicity of the solvent very much affects the catalytic activity, so Raney Ni in nonbasic solvents is an extremely active catalyst for hydrogenolysis and hydrogenation. In basic solvents, however, Raney Ni is a less active, but much more selective catalyst for hydrogenolysis while preserving the aromatic products. With regard to the reactions with lignin, assessing the complexity of the product mixtures by two-dimensional GC x GCMS revealed solvent effects on the product distribution. Reaction in methylcyclohexane resulted in cyclic alcohols and cyclic alkanes, whereas reaction in 2-propanol led to cyclic alcohols, cyclic ketones, and unsaturated products. The hydrogenolysis of lignin in methanol, however, produced mostly phenols. Overall, these results demonstrate that the solvent plays a key role in directing the selectivity and, thus, it must be taken into consideration in the design of catalytic systems for conversion of lignin by hydrogenolysis of C-O ether bonds.