Tuning thermal and graphitization behaviors of lignin complexation with transition metal ions for the synthesis of multilayer graphene-based materials.

Thermal conversion of kraft lignin, an abundant renewable aromatic substrate, into advanced carbon materials including graphitic carbon and multilayer/turbostratic graphene has recently attracted great interest. Our innovative catalytic upgrading approach integrated with molecular cracking and welding (MCW) enables mass production of lignin-derived multilayer graphene-based materials. To understand the critical role of metal catalysts in the synthesis of multilayer graphene, this study was focused on investigating the effects of transition metals (, molybdenum (Mo), nickel (Ni), copper (Cu), and iron (Fe)) on thermal and graphitization behaviors of lignin. During the preparation of metal-lignin (M-lignin) complexes, Fenton-like reactions were observed with the formation of Fe- and Cu-lignin complexes, while Ni ions strongly interacted with oxygen-containing surface functional groups of lignin and Mo oxyanions weakly interacted with lignin through ionic bonding. Different chelation mechanisms of transition metal ions with lignin influenced the stabilization, graphitization, and MCW steps involved in thermal upgrading. The M-lignin complex behaviors in each of the three steps were characterized. It was found that multilayer graphene-based materials with nanoplatelets can be obtained from the Fe-lignin complex MCW operation at 1000 °C under methane (CH). Raman spectra indicated that Fe- and Ni-lignin complexes experienced a higher degree of graphitization than Cu- and Mo-lignin complexes during thermal treatment.