Innovative Long-Lasting Catalytic Hydrothermal Reaction for High Efficient Energy Harvest and Carbon Capture from Recalcitrant Wastewater.

Simultaneous recovery of energy and carbon from recalcitrant wastewater has attracted ever-growing interest for water management. However, the existing technologies to break down recalcitrant pollutants are mainly energy and chemical intensive. Here, a novel hydrothermal reaction amended with activated carbon (AC) was demonstrated to enable an unprecedented 99.5% removal of an exemplar difficult-to-degrade contaminant, polyvinyl alcohol (PVA), from wastewater. Meanwhile, an easy-separated hydrochar (C6H7.08O0.99) with an abundance of unsaturated aromatic rings was produced, exhibiting 118.46% of energy yield with a high heating value of 32.9 MJ/kg, outperforming the hydrochar(s) reported to date. The retrieved energy from the hydrochar was able to entirely offset the energy needs for this hydrothermal process. Interestingly, the AC catalyst can sustain in situ reuse over 125 cycles with no evidence of irreversible deactivation. The adjacent carbonyl groups on AC were revealed to provide active sites for dehydrogenation from either the C-H (1.24 Å) or O-H (1.40 Å) bond in PVA, forming hydroxyl groups on AC and highly reactive intermediates (ΔG0 = -11.5 kcal/mol). It was further proved that the free oxygen in the headspace extracted H atoms from the newly formed hydroxyl groups on AC (ΔG0 = -4.7 kcal/mol), thus regenerating the carbonyl sites on AC for the next catalytic hydrothermal dehydrogenation cycles. The long-lasting catalyst reusability and energy self-sufficient approach offer a sustainable route to carbon neutrality in recalcitrant wastewater treatment.