Totally green cellulose conversion into bio-oil and cellulose citrate using molten citric acid in an open system: synthesis, characterization and computational investigation of reaction mechanisms.

The simultaneous transformation of crystalline or amorphous cellulose into a furan-based bio-oil and cellulose citrate was realized avoiding the use of strong inorganic acids, drastic conditions, enzymatic treatments or microorganism fermentation. This innovative method is very eco-friendly and involves the use of molten citric acid under solvent free conditions at atmospheric pressure. An accurate discussion on chemical composition of the bio-oil enriched in bioprivileged molecules as well as structural and morphological characterization of cellulose citrate was reported. Moreover, mechanistic hypotheses were formulated on the basis of experimental findings and detailed DFT quantum-mechanical simulations were carried out to confirm, step by step, the proposed reaction paths.