Oxidative Cleavage of α-O-4, β-O-4, and 4-O-5 Linkages in Lignin Model Compounds Over P, N Co-Doped Carbon Catalyst: A Metal-Free Approach.

Developing efficient metal-free catalysts for lignin valorization is essential but challenging. In this study, a cost-effective strategy is employed to synthesize a P, N co-doped carbon catalyst through hydrothermal and carbonization processes. This catalyst effectively cleaved α-O-4, β-O-4, and 4-O-5 lignin linkages, as demonstrated with model compounds. Various catalysts were prepared at different carbonization temperatures and thoroughly characterized using techniques such as XRD, RAMAN, FTIR, XPS, NH 3 -TPD, and HRTEM. Attributed to higher acidity, the P 5 NC-500 catalyst exhibited the best catalytic activity, employing H 2 O 2 as the oxidant in water. Additionally, this metal-free technique efficiently converted simulated lignin bio-oil, containing all three linkages, into valuable monomers. Density Functional Theory calculations provided insight into the reaction mechanism, suggesting substrate and oxidant activation by P-O-H sites in the P 5 NC-500, and by N-C-O-H in the CN catalyst. Moreover, the catalyst's recyclability and water utilization enhance its environmental compatibility, offering a highly sustainable approach to lignin valorization with potential applications in various industries.