Biomimetic Geminal-Atom Catalysts Empowered by Jahn–Teller Distortion: A Theoretical Study for Efficient PET Degradation

Inspired by the structural elegance and catalytic precision of binuclear metalloenzymes, we computationally designed a series of biomimetic geminal-atom catalysts incorporating biologically abundant first-row transition metals (Fe, Co, Ni, Cu, Zn) to achieve efficient polyethylene terephthalate (PET) hydrolysis. Systematic investigations using density functional theory calculations were carried out to thoroughly evaluate not only the key kinetic steps but also the complete catalytic cycles, including adsorption, reaction, and desorption processes for each catalyst. These studies revealed that the M₂(μN)₂N₄@C type catalysts significantly outperform their M₂(N₃)₂@C analogues due to enhanced electrophilic activation of ester substrates. Notably, the Cu₂(μN)₂N₄@C catalyst exhibited an exceptionally low energy barrier (0.23 eV), comparable to those of natural enzymes. Detailed electronic structure analyses unambiguously identified Jahn-Teller distortion-induced orbital reorganization as the key mechanism underpinning Cu₂(μN)₂N₄@C's extraordinary catalytic activity. Our findings provide a comprehensive mechanistic understanding of the catalytic pathway, and underscore the crucial impact of coordination environment and electronic structure on PET hydrolysis efficiency, thus offering valuable guidance for rational design of next-generation plastic-degrading catalysts.