Selectively Steering the Retention and Cleavage of C–C Bond in Electrooxidation of PET Plastic and Biomass-Derived Alcohols by Defective Ni(OH)_2–<i>x</i>-Supported Pt

Electrocatalytic upgrading of plastic waste and biomass into value-added chemicals offers a sustainable approach for resource utilization. However, it remains challenging to realize adjustable and efficient C–C activation behavior during electrooxidation. Herein, by designing Pt@Ni(OH)2–x electrocatalyst consisting of Ni–O–Pt interface and abundant oxygen vacancies, the intelligent switchover between C–C maintained and broken products was successfully achieved in electrooxidation of ethylene glycol (EG from PET) and glycerol (GLY from biodiesel). Especially, for EG electrooxidation, Pt@Ni(OH)2–x delivers remarkable selectivity and activity toward C2 (CH2OHCOOH) and C1 (HCOOH) (95 and 92%, respectively) with industrial-scaled current densities at moderate potentials (355.1 mA cm–2 at 0.9 V and 382.3 mA cm–2 at 1.6 V, respectively). Experimental and theoretical results reveal that (1) the tunable C–C activation ability strongly depends on the oxidation state of Pt@Ni(OH)2–x, and *CH2OHCOOH intermediate is the key factor determining the selectivity of C2 and C1; (2) the strong coupling interface induced by Ni–O–Pt bridge and oxygen vacancies activate the synergistic effect, enriching EG and OH–, and facilitating the reversibility of Ni2+/Ni3+ species. Additionally, a solar-powered reactor with an Internet system was designed for upcycling real-world PET bottles, which realized the controllable switchover between C1 and C2 products by “one click”. This study underlines the tunable C–C activation capability, laying the way for the design of bifunctional catalysts toward polyhydric alcohol electrooxidation.