Charge Confinement in an Ordered High-Entropy Intermetallic Breaks the Activity-Poisoning Trade‑Off for Glycolic Acid Electrosynthesis From Polyethylene Terephthalate.

Yang, Ruidong; Geng, Jiabing; Yu, Jiabao; Xiao, Ningxin; Deng, Kai; Yin, Shibin; Wang, Liang; Yu, Hongjie et al. · Adv Mater · 2026

basic_science · Level V

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Abstract

Selective electrooxidation of ethylene glycol (EG) from polyethylene terephthalate (PET) hydrolysate to glycolic acid (GA) offers a sustainable route for plastic upcycling but is hindered by insufficient activity at industrially relevant current densities and severe catalyst deactivation caused by poisoning intermediates. Here, we design a two-dimensional ordered high-entropy intermetallic, HEI (PdPtRh)(InBi)ene, based on a Pd<sub>1</sub>In<sub>1</sub>-type body-centered-cubic framework. The ordered lattice induces pronounced p--d hybridization and charge redistribution, giving rise to a charge-confinement effect at the active sites. Operando infrared spectroscopy, CO stripping, and theoretical calculations reveal that this confined electronic environment precisely regulates the evolution of the key poisoning intermediate *COCH<sub>2</sub>OH, weakening its accumulation while preserving efficient EG activation. As a result, HEI (PdPtRh)(InBi)ene achieves a current density of 554.21 mA cm<sup>-2</sup> at 0.9 V in PET hydrolysate (PETH). Furthermore, it maintains stable operation for 90 h in a flow cell at an industrially relevant current density of 200 mA cm<sup>-2</sup>, delivering an average GA Faradaic efficiency of 99.22% and an average GA production rate of 1.85 mmol h<sup>-1</sup> cm<sup>-2</sup>. These findings demonstrate charge-confinement engineering as an effective route to regulate poisoning-intermediate behavior in electrocatalytic alcohol oxidation.