Bioinspired Asymmetric W-O-Ni Active Centers for Selective Electrochemical Upcycling of Polyethylene Terephthalate

Electrochemical upcycling of waste PET into value-added formate • Soybean root-inspired design of symbiotic active sites • Oxygen-bridge-induced 3d-5d orbital hybridization The efficient transformation of waste poly(ethylene terephthalate) (PET) into high-value chemicals represents a pivotal strategy toward a circular plastics economy. Drawing inspiration from the cooperative nitrogen-fixation relationship between rhizobia and leguminous plants, we report a tungsten-modified nickel phosphide (W-Ni 2 P) catalyst for the selective electrooxidation of PET-derived ethylene glycol (EG) into formic acid (FA). Upon electrochemical activation, robust asymmetric W-O-Ni oxygen-bridged configurations are formed in situ, establishing cooperative catalytic centers in which W operates as an electronic modulator while Ni serves as the dominant active site. The tungsten centers display strong adsorption toward *EG and *OH intermediates, functioning as dynamic buffering sites that regulate the interfacial microenvironment and concurrently facilitate the reconstruction of Ni into highly active oxyhydroxide species. This synergistic interplay, governed by W-O-Ni-mediated 3d-5d orbital interactions, effectively reduces the kinetic barriers associated with C-H dehydrogenation and C-C bond cleavage. Consequently, the optimized W-Ni 2 P catalyst achieves a current density of 500   mA   cm -2 at 1.45   V versus RHE, delivering a Faradaic efficiency of 98.9% for FA production. Moreover, an anion-exchange-membrane electrolyzer sustains stable operation for over 200   hours in authentic PET hydrolysate, highlighting the system’s practical durability, scalability, and economic potential for plastic waste upcycling. Download: Download high-res image (212KB) Download: Download full-size image Inspired by rhizobium-legume symbiosis, W was incorporated into Ni 2 P to form cooperative W-O-Ni active sites, which facilitate Ni reconstruction, optimize intermediate adsorption, lower EGOR energy barriers, and promote highly efficient formic acid production from PET waste.