Yeast Inherited Phosphide/Bio‐Carbon for Controllable Polyethylene Terephthalate Upcycling

Abstract Electrochemical reforming of polyethylene terephthalate (PET) coupled with hydrogen production is of great significance to realize the sustainable development of clean energy technologies. Nevertheless, precisely controlling the reaction pathways and selectively converting key intermediates during glycol oxidation reaction (EGOR) pose considerable challenges. Herein, theoretical calculations and experiments reveal that the key intermediate (*CHO‐CHO) and the role of P in promoting the reconstruction of transition metal phosphides surface during the EGOR process. Consequently, the bio‐template strategy is introduced to design bimetal phosphide@bio‐carbon pre‐catalyst toward efficient EGOR and hydrogen evolution reaction (HER). This design enables controlled *CHO‐CHO intermediate formation and transformation through the enhanced adsorption of OH* and *CHO‐CHO, leading to a highly selective EGOR. The C1 product of formic acid exhibits superior Faradaic efficiency (99.1%) at 1.35 V. In addition, this constructed catalyst only requires 1.76 V@500 mA cm −2 and can stably perform for more than 240 h at 500 mA cm −2 toward EGOR coupled with HER in the PET hydrolysate. This work proposes a novel strategy to construct superior catalyst for efficient PET upcycling coupled with HER, which is crucial to the sustainable development of multidisciplinary integration with biology and clean energy conversion technologies.