Alcoholysis of poly(ethylene terephthalate) (PET) waste to produce monomers, including methanolysis to yield dimethyl terephthalate (DMT) and glycolysis to generate bis-2-hydroxyethyl terephthalate (BHET), is a promising strategy in PET waste management. Here, we introduce an efficient PET-alcoholysis approach utilizing an oxygen-vacancy (V_o)-rich catalyst under air, achieving space time yield (STY) of 505.2 g_DMT·g_cat⁻¹·h⁻¹ and 957.1 g_BHET·g_cat⁻¹·h⁻¹, these results represent 51-fold and 28-fold performance enhancements compared to reactions conducted under N₂. In situ spectroscopy, in combination with density functional theory calculations, elucidates the reaction pathways of PET depolymerization. The process involves O₂-assisted activation of CH₃OH to form CH₃OH^* and OOH^* species at V_o-Zn²⁺–O–Fe³⁺ sites, highlighting the critical role of V_o-Zn²⁺–O–Fe³⁺ sites in ester bond activation and C–O bond cleavage. Moreover, a life cycle assessment demonstrates the viability of our approach in closed-loop recycling, achieving 56.0% energy savings and 44.5% reduction in greenhouse-gas emissions. Notably, utilizing PET textile scrap further leads to 58.4% reduction in initial total operating costs. This research offers a sustainable solution to the challenge of PET waste accumulation.

聚对苯二甲酸乙二醇酯 (PET) 废物醇解生产单体，包括甲醇解生产对苯二甲酸二甲酯 (DMT) 和糖酵解生产对苯二甲酸双-2-羟乙酯 (BHET)，是 PET 废物管理的一种有前景的策略。在这里，我们介绍了一种在空气下利用富氧空位（V _o ）催化剂的高效 PET 醇解方法，实现了 505.2 g _DMT ·g 的时空产率（STY） _cat ⁻¹ ·h ⁻¹ 和 957.1 g _BHET ·g _cat ⁻¹ · h ⁻¹ ，与 N ₂ 下进行的反应相比，这些结果代表性能提高了 51 倍和 28 倍。原位光谱结合密度泛函理论计算，阐明了 PET 解聚的反应途径。该过程涉及 O ₂ 辅助活化 CH ₃ OH 形成 CH ₃ OH ^* 和 OOH ^* V _o -Zn ²⁺ –O–Fe ³⁺ 位点上的物种，突出了 V _o -Zn ²⁺ –O–Fe ³⁺ 酯键活化和 C-O 键裂解位点。此外，生命周期评估证明了我们的闭环回收方法的可行性，实现了 56.0% 的能源节约和 44.5% 的温室气体排放减少。值得注意的是，利用 PET 纺织废料进一步使初始总运营成本降低 58.4%。这项研究为应对 PET 废物堆积的挑战提供了可持续的解决方案。