Breaking the lignin conversion bottleneck for multiple products: Co-production of aryl monomers and carbon nanospheres using one-step catalyst-free depolymerization

• A one-step catalyst-free depolymerization strategy for lignin conversion is developed. • CH 2 Cl 2 /MAD system produces aryl monomers and carbon nanospheres with 63.4 wt% yield. • Hydrogen radicals and HCl in-situ formed from CH 2 Cl 2 can reform the pyrolysis vapors. • Carbon nanospheres are formed by the surface erosion and decrease in surface energy. Lignin is considered as a renewable and sustainable resource for producing value-added aromatic chemicals and functional carbon materials. Herein, we develop a one-step catalyst-free depolymerization strategy to convert lignin into aryl monomers and carbon nanospheres simultaneously. Importantly, microwave-assisted depolymerization (MAD) in conjunction with dichloromethane (CH 2 Cl 2 ) vapors is developed. The total mass yield of guaiacols reached the highest amount of 225.1 mg/g at 600 °C, and the highest yields of phenols (49.0 mg/g) and aromatic hydrocarbons (155.1 mg/g) were obtained at 700 °C. Hydrogen radicals and hydrogen chloride (HCl) are in-situ formed from CH 2 Cl 2 , significantly decreasing the activation barrier and reforming pyrolysis vapors to promote the formation of aryl monomers. Interestingly, uniform carbon nanospheres with an average size of 140 nm were produced as co-products at 700 °C. The microwave "hot-spots", allied with the continuous surface erosion and the decrease in surface energy of lignin-derived carbon precursors by CH 2 Cl 2 vapor, can be considered the driving force for the ultimate formation of carbon nanospheres. The CH 2 Cl 2 /MAD system produces aryl monomers (26.8 wt% yield) and carbon nanospheres (36.6 wt% yield) at 700 °C. We provide a facile, intriguing and scalable approach to convert lignin to valuable aryl monomers and sustainable carbon materials that can be applied in the chemistry, energy and environmental fields.