Low‐Energy Catalytic Electrolysis for Simultaneous Hydrogen Evolution and Lignin Depolymerization

Abstract Here, a new proton‐exchange‐membrane electrolysis is presented, in which lignin was used as the hydrogen source at the anode for hydrogen production. Either polyoxometalate (POM) or FeCl 3 was used as the catalyst and charge‐transfer agent at the anode. Over 90 % Faraday efficiency was achieved. In a thermal‐insulation reactor, the heat energy could be maintained at a very low level for continuous operation. Compared to the best alkaline–water electrolysis reported in literature, the electrical‐energy consumption could be 40 % lower with lignin electrolysis. At the anode, the Kraft lignin (KL) was oxidized to aromatic chemicals by POM or FeCl 3 , and reduced POM or Fe ions were regenerated during the electrolysis. Structure analysis of the residual KL indicated a reduction of the amount of hydroxyl groups and the cleavage of ether bonds. The results suggest that POM‐ or FeCl 3 ‐mediated electrolysis can significantly reduce the electrolysis energy consumption in hydrogen production and, simultaneously, depolymerize lignin to low‐molecular‐weight value‐added aromatic chemicals.