Li Zhonghua, Chen Ping, Feng Jianyong, Zhao Minyue, Zhao Zongyan, Zhang Yuanming, Xu Xiaoming, Huang Huiting, Zou Zhigang, Li Zhaosheng
National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing, 210093, China.
Jiangsu Key Laboratory for Nano Technology, Nanjing University, Nanjing, 210093, China.
Angew Chem Int Ed Engl. 2024 Sep 9;63(37):e202409876. doi: 10.1002/anie.202409876. Epub 2024 Aug 8.
Lattice-oxygen activation has emerged as a popular strategy for optimizing the performance and selectivity of oxide-based thermocatalysis and electrolysis. However, the significance of lattice oxygen in oxide photocatalysts has been ignored, particularly in gas-solid reactions. Here, using methane oxidation over a Ru@ZnO single-atom photocatalyst as the prototypical reaction and via O isotope labelling techniques, we found that lattice oxygen can directly participate in gas-solid reactions. Lattice oxygen played a dominant role in the photocatalytic reaction, as determined by estimating the kinetic constants in the initial stage. Furthermore, we discovered that dynamic diffusion between O and lattice oxygen proceeded even in the absence of targeted reactants. Finally, single-atom Ru can facilitate the activation of adsorbed O and the subsequent regeneration of consumed lattice oxygen, thus ensuring high catalyst activity and stability. The results provide guidance for next-generation oxide photocatalysts with improved activities and selectivities.
晶格氧活化已成为优化氧化物基热催化和电解性能及选择性的常用策略。然而，晶格氧在氧化物光催化剂中的重要性一直被忽视，尤其是在气固反应中。在此，以Ru@ZnO单原子光催化剂上的甲烷氧化作为典型反应，并通过氧同位素标记技术，我们发现晶格氧可直接参与气固反应。通过估算初始阶段的动力学常数确定，晶格氧在光催化反应中起主导作用。此外，我们发现即使在没有目标反应物的情况下，氧与晶格氧之间也会发生动态扩散。最后，单原子Ru可促进吸附氧的活化以及消耗的晶格氧的后续再生，从而确保高催化剂活性和稳定性。这些结果为具有更高活性和选择性的下一代氧化物光催化剂提供了指导。
