Fig. 4: Radical reaction mechanism of polyolefin depolymerization.

a DFT-derived bonding energies of internal C–C/C–H bond energies in C10H22 and the activation enthalpy of β-C–C bond scission, β-C–H bond scission, and β-H rearrangement of C10H21· radical with the DFT-optimized transition state structures insert. b DFT-derived reaction free energy diagrams for C10H21· decomposition at 1250 °C and 1 atm. c The temperature dependences of ΔG for the generation of C2H4, C10H20, and C3H8 from C10H21·, generation of CH4 from C10H22 and H·, and dehydrogenation of C2H4 to C2H2.