Concurrent CO2 and plastic waste photocarbovalorizing into fuels using an orbital-engineered high-entropy oxide photocatalyst.

While achieving carbon neutrality remains challenging because of continued usage of fossil fuels and plastics, the conversion of CO to fuels and the upcycling of plastic waste into valuable products present a major opportunity to valorize carbon. This research enhances the value of carbon concurrently in two pollutants, CO and plastic waste, using light, a process we name photocarbovalorizing. A high-entropy oxide photocatalyst is designed for this process, incorporating f cations (lanthanum and cerium), known for high CO adsorption capacity, alongside d (tantalum and niobium) and d (zinc) cations for their photocatalytic proficiency. The coexistence of these cations positively generates a heterogeneous electronic structure, facilitates charge separation and transfer, induces oxygen vacancies, and generates lattice strain (confirmed by synchrotron X-ray absorption spectroscopy). The oxide demonstrates CO photoreduction to CO and CH; however, concurrent introduction of polyethylene terephthalate (PET) plastic waste not only enhances CO and CH production by 2.5-3.3 times but also produces value-added organic chemicals, such as ethylene glycol and acetic acid, from PET degradation. Beyond introducing high-entropy oxides with mixed f-d-d orbitals as new photocatalysts, these findings establish a process of photocarbovalorizing for the cooperative CO and plastic waste conversion.