Modeling Study of Woody Biomass: Interactions of Cellulose, Hemicellulose, and Lignin

Lignocellulosic biomass pretreatment and the subsequent thermal conversion processes to produce solid, liquid, and gas biofuels are attractive solutions for today’s energy challenges. The structural study of the main components in biomass and their macromolecular complexes is an active and ongoing research topic worldwide. The interactions among the three main components, cellulose, hemicellulose, and lignin, are studied in this paper using electronic structure methods, and the study includes examining the hydrogen bond network of cellulose–hemicellulose systems and the covalent bond linkages of hemicellulose–lignin systems. Several methods (semiempirical, Hartree–Fock, and density functional theory) using different basis sets were evaluated. It was shown that theoretical calculations can be used to simulate small model structures representing wood components. By comparing calculation results with experimental data, it was concluded that B3LYP/6-31G is the most suitable basis set to describe the hydrogen bond system and B3LYP/6-31G(d,p) is the most suitable basis set to describe the covalent system of woody biomass. The choice of unit model has a much larger effect on hydrogen bonding within cellulose–hemicellulose system, whereas the model choice has a minimal effect on the covalent linkage in the hemicellulose–lignin system.