Oxygen vacancy engineering has been verified as an important approach to achieve the efficient degradation of VOCs in nanomaterials. Herein, a synthetic strategy of Pt-CeO₂/MnO₂ hetero-catalysts is developed to fine-manipulate the surface oxygen vacancies and catalytic activities through surface CeO₂ decoration as a surface O-vacancy donor. Among these Pt-based catalysts, the optimal Pt-0.15Ce-Mn catalyst exhibits the greatest catalytic activity for toluene oxidation (T₉₉=155 °C), which is attributed to more oxygen vacancies, outstanding redox ability and well dispersion of Pt. Combined with experiments and DFT calculations, it has been demonstrated that the special role of introducing CeO₂ NPs is to induce the generation of more O-vacancies, new structure defects (Mn³⁺ and Ce³⁺ species), and the lower formation energy of oxygen vacancy. Furthermore, the synergistic effect of dual O-vacancies (surface decorated and intrinsic O-vacancies) via an oxygen replenishment-migration pathway is the key to boost the remarkable catalytic activity for deep toluene oxidation. Finally, in situ DRIFTS reveals that partial toluene molecules can be adsorbed directly on surface adsorbed oxygen species replenished by gas-phase oxygen, and these catalysts with richer O-vacancies can effectively reduce the accumulation of by-product (phenolate, C₆H₅–OH).

氧空位工程已被验证为实现纳米材料中VOC有效降解的重要方法。本文中，开发了Pt-CeO ₂ / MnO ₂杂催化剂的合成策略以通过作为表面O-空位供体的表面CeO ₂装饰来精细地控制表面氧空位和催化活性。在这些基于Pt的催化剂中，最佳的Pt-0.15Ce-Mn催化剂表现出最大的甲苯氧化催化活性（T ₉₉ = 155°C），这归因于更多的氧空位，出色的氧化还原能力和Pt的良好分散性。结合实验和DFT计算，已证明引入CeO ₂的特殊作用NPs可以诱导产生更多的O空位，新的结构缺陷（Mn ³⁺和Ce ³⁺物种）以及较低的氧空位形成能。此外，通过氧气补充-迁移途径的双重O-空位（表面修饰的和固有的O-空位）的协同效应是提高深层甲苯氧化显着催化活性的关键。最后，原位DRIFTS表明，部分甲苯分子可以直接吸附在气相氧补充的表面吸附氧物种上，这些具有更丰富的O空位的催化剂可以有效地减少副产物（酚盐，C ₆ H _5）的积累。-哦）。