Diluted Alkaline Pretreatment in Hexafluoroisopropanol Facilitates Chemoenzymatic Depolymerization of Polyethylene Terephthalate

Enzymatic PET degradation presents a sustainable and eco-friendly solution for recycling and upgrading PET materials. While various PET-degrading enzymes have proven effective in converting low-crystallinity PET into monomers, their efficiency decreases significantly for high-crystallinity PET. Given that most commercially available PET products are highly crystalline and have a limited specific surface area, conventional methods typically resort to heat treatment and ball milling to achieve decrystallization and micronization before enzymatic hydrolysis. However, these pretreatments often compromise environmental benefits due to their high energy consumption and dust pollution, and are difficult to scale up. In this study, we developed a chemoenzymatic strategy that efficiently depolymerizes waste PET materials into monomers in just 4 hours. This process involves an alkaline treatment with diluted NaOH in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), followed by enzymatic hydrolysis of the PET nanosuspensions generated from solvent exchange. The alkaline treatment partially breaks down the PET molecular chains and mitigates recrystallization during the precipitation process. Importantly, the complete hydrolysis of PET is attributed to reduced crystallinity rather than particle size. Notably, this method eliminates the need for PET micronization and minimizes the usage of NaOH. The effectiveness of this method was demonstrated through the hydrolysis of various commercially available PET products, showcasing its potential to advance enzymatic degradation processes for PET recycling.