Atomic Cu–O–Zr Sites for Highly Selective Production of <i>p</i> ‐xylene from Tandem Upcycling of PET and CO ₂

Abstract Exploring an efficient catalytic system for tandem upcycling of CO 2 and polyethylene terephthalate (PET) is highly desirable for achieving efficient resource utilization of wastes. However, the high activation energy for C═O bonds (in both PET and CO 2 ) and the difficulty in regulating the reaction pathways restricted PET recovery efficiency. Here, we demonstrated the rational design of a single‐atom Cu catalyst for precisely catalyzing the hydrogenation of CO 2 to methanol and tandem PET upcycling to ethylene glycol (EG) and p ‐xylene (PX). In the Cu/UiO‐66‐NH 2 ‐A catalyst, Cu atoms are selectively anchored to the Zr‐oxo nodes of UiO‐66‐NH 2 to form Cu–O–Zr sites. The Cu–O–Zr sites can effectively activate both CO 2 and H 2 by reducing the activation energy and accelerate the transformation of PET to dimethyl terephthalate (DMT), which is further hydro‐deoxygenated to yield PX. As a result, 20.4% CO 2 conversion was obtained within 36 h, with 89.5% and 92.1% yields of PX and EG, respectively. Rapid and precise hydrogen spillover from Cu atoms to adsorbed reactants/intermediates at the Cu–O–Zr sites also drives the reaction process.