Zinc Vacancy Promotes Photo‐Reforming Lignin Model to H2 Evolution and Value‐Added Chemicals Production.

Lignin, rich in β‐O‐4 bonds and aromatic structure, is a renewable and potential resource for value‐added chemicals and promoting H2 evolution. However, direct photo‐reforming lignin remains a huge challenge due to its recalcitrant structure. Herein, a collaborative strategy is proposed by dispersing Pt on zinc‐vacancy‐riched ZnIn2S4 (Pt/VZn‐ZIS) for revealing the effect of lignin structure during photo‐reforming process with lignin models. And a series of theoretical calculations and experimental results show that lignin model substances with more nucleophilic group structures will have a stronger tendency to occur the photo‐reforming reactions. In addition, benefiting of Pt‐S electronic channel is formed by occupying Pt atom onto zinc vacancies in ZnIn2S4, which can effectively reduce the energy barrier of H2 evolution and accompany the selective oxidation of lignin model from Cα‐OH to Cα = O under simulated sunlight. The natural lignin is used to further demonstrate this selective oxidation mechanism. The presented work demonstrates the photo‐reforming lignin model mechanism and the influence of lignin‐structure during the process of photo‐reforming. [ABSTRACT FROM AUTHOR]