Recent Advances in Cellulose Depolymerization: Mechanistic Insights, Catalytic Innovations, and Scalable Pathways for Biomass Valorization.

Cellulose is the most promising abundant renewable polymer material with the highest potential for the future low-carbon biorefineries. However, its utilization in industry is limited by the structural recalcitrance as a result of organization of crystalline domains, fibrillar architecture hierarchy and intramolecular and intermolecular hydrogen bonding which is responsible for access restriction for the catalysts and consequent cleavage of the glycosidic bonds. Therefore, efficient depolymerization of cellulose is of paramount importance as a step in biomass conversion into the low molecular products. In this review, the recent advances in cellulose depolymerization are discussed. The chemical, enzymatic, thermal, thermochemical, mechanochemical, oxidative and hybrid catalytic method is thoroughly discussed. Attention is paid to the mechanism of the depolymerization reaction steps as glycosidic bond activation as hydrolytic, radical mediated, and energy assisted pathways. Selectivity and conversion efficiency based on substrate morphology, solvent system and catalyst design are also discussed. Further, there is a comparison of key performance metrics which are relevant for the industrial process as product yield, carbon efficiency, energy demand, stability of the catalyst, solvent recyclability and impact to the environmental lifecycle. The pros and cons of the various methods are also represented. Processes based on mineral acids enable rapid conversion. However, they suffer from corrosion, waste handling issues and degradation by-products. On the other hand, enzymatic depolymerization processes offer relatively high selectivity but they are limited in terms of feedstock sensitivity and slow reaction kinetics. The downstream valorization mechanisms are also described with the result being that no single available technology is capable of satisfying all industrial requirements. Thus, future progress expects integrated circular processes where advanced catalysis, process intensification and digital optimization strategies take place.