Upcycling Waste Expanded Polystyrene into Fe@Graphitic-Carbon Catalysts for Glycolytic Recycling of PET to BHET

Chemical glycolysis can convert waste poly(ethylene terephthalate) (PET) into bis(2-hydroxyethyl) terephthalate (BHET), but recyclable heterogeneous catalysts derived from circular carbon sources and showing low metal release remain limited. Here, post-consumer expanded polystyrene (EPS) was transformed into a hypercrosslinked polymer (HCP) and carbonized with Fe to produce Fe@graphitic-carbon (Fe@C) catalysts for PET glycolysis. The catalysts are denoted mFe@EPS-HCP₈₀₀, where m represents the nominal Fe loading (wt.%), and 800 is the carbonization temperature (°C). The optimized 5Fe@EPS-HCP₈₀₀ contained graphitic carbon layers, bamboo-like carbon nanotube (CNT) domains, hierarchical porosity, and Fe-rich domains associated with graphitic carbon coverage. Under atmospheric-pressure conditions (PET, 2.00 g; ethylene glycol, 20.00 g; catalyst, 0.20 g; 200 °C; 2 h), it achieved complete PET conversion and 94.6% BHET yield. The catalyst also maintained BHET yields of ca. 90-94% over ten reuse runs, and post-reaction microscopy confirmed the retention of graphitic carbon layers and Fe-containing domains. Fe was below the detection limit in the product solutions for the 1, 3, and 5 wt.% Fe catalysts, whereas 7Fe@EPS-HCP₈₀₀ released 9.1 mg kg^-1 Fe, consistent with incomplete carbon coverage at excessive Fe loading. Conversion profiles followed an Avrami-Erofeev/Weibull model, giving an apparent activation energy of 205.6 kJ mol^-1. The data support a two-stage pathway in which external graphitic carbon/CNT domains promote primary PET chain scission to soluble oligomers, followed by Fe@C interfacial secondary glycolysis to BHET. This work demonstrates dual waste-polymer valorization by using EPS waste as catalytic infrastructure for PET chemical recycling.