Binary Iron‐Manganese Cocatalyst for Simultaneous Activation of C‐C and C‐O Bonds to Maximally Utilize Lignin for Syngas Generation over InGaN

Abstract Solar‐powered lignin reforming offers a carbon‐neutral route for syngas production. This study explores a dual non‐precious iron‐manganese cocatalyst to simultaneously activate both C−C and C−O bonds for maximizing the utilization of various substituents of native lignin to yield syngas. The cocatalyst, integrated with InGaN nanowires on a Si wafer, affords a measurable syngas evolution rate of 42.4 mol g cat −1 h −1 from native lignin in distilled water with a high selectivity of 93 % and tunable H 2 /CO ratios under concentrated light, leading to a considerable light‐to‐fuel efficiency of 11.8 %. The high FeMn atom efficiency arising from the 1‐dimensional nanostructure of InGaN enables the achievement of a high turnover frequency (TOF) of 220896 mol syngas per mol FeMn per hour. Combined experimental and theoretical investigations reveal that the synergetic iron‐manganese cocatalyst supported by InGaN nanowires enables simultaneous activation of C−C and C−O bonds with comparable minimized dissociation energies, thus promising to maximally utilize different substituents of −OCH 3 , and −CH 2 CH 2 CH 3 in lignin for syngas production. Moreover, the dual Fe‐Mn cocatalyst demonstrates a most energetically favorable route for the consecutive release of hydrogen from •CH 3 and •OH by the oxidative holes while inhibiting the reversion of hydrogen and hydroxyl into water.