Competitive effects of glucan’s main hydrolysates on biochar formation: A combined experiment and density functional theory analysis

[Display omitted] •Clarify the competitive effects of glucan’s main hydrolysates on biochar formation.•5-HMF, FA, and LA are involved in biochar formation, especially 5-HMF.•Etherification of 5-HMF itself occurs firstly and is key to form biochar.•Reactions of 5-HMF and FA, 5-HMF and LA are important for biochar formation. The complexity of polysaccharide hydrothermal products increases the difficulty of exploring the formation of biochar, limiting the development of biochar. This work clarifies the completive effects of glucan’s main hydrolysates on biochar formation from three aspects: experimental, thermodynamic, and kinetic. The products distribution illustrates that 5-HMF, FA, and LA are mainly involved in the formation of biochar. Biochar mainly includes furan ring, ether group, and ester group by the analysis of magic-angle-spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, and elemental analysis. Combined experiments and density functional theory analysis, the etherification reaction of 5-HMF itself is most likely to occur and is key to form biochar, followed by the esterification of FA with 5-HMF, and then the etherification of 5-HMF and LA. The further verified experiments also manifest these results. This work will develop a foundation for exploring the complex formation mechanism of cellulose-based biochar.