Liu Hao, Yang Shan, Mi Jinxing, Sun Chuanzhi, Chen Jianjun, Li Junhua
School of Environment, Tsinghua University, Beijing 100084, P. R. China.
College of Geography and Environment, Shandong Normal University, Jinan 250014, P. R. China.
Environ Sci Technol. 2024 Sep 11. doi: 10.1021/acs.est.4c02277.
NO and CO coexist in various industrial and mobile sources. The synergistic reaction of NO and CO to generate N and CO has garnered significant research interest, but it remains extremely challenging. Herein, we constructed an atomically dispersed Rh-supported CeO catalyst with asymmetric Rh-O-Ce sites through gradient Rh 4d-O 2p-Ce 4f orbital coupling. This design effectively regulates the 4f electron states of Ce and promotes the electron filling of the O 3π* antibonding orbital to facilitate N-O bond cleavage. Near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) reveals that CO reacts with the surface-adsorbed O* generated by NO decomposition through self-tandem catalysis, accelerating the rate-limiting step in NO decomposition and activating the synergistic reaction of NO and CO at temperatures as low as 115 °C. This work can guide the development of high-performance catalysts using the strategy of high-order orbital hybridization combined with the tandem concept to achieve versatile catalytic applications.
一氧化氮（NO）和一氧化碳（CO）共存于各种工业和移动源中。NO与CO发生协同反应生成氮气（N）和二氧化碳（CO₂），这一反应已引起了广泛的研究兴趣，但仍然极具挑战性。在此，我们通过梯度Rh 4d-O 2p-Ce 4f轨道耦合构建了具有不对称Rh-O-Ce位点的原子分散Rh负载CeO催化剂。这种设计有效地调节了Ce的4f电子态，并促进了O 3π反键轨道的电子填充，从而有利于N-O键的断裂。近常压X射线光电子能谱（NAP-XPS）表明，CO通过自串联催化与由NO分解产生的表面吸附O反应，加速了NO分解中的限速步骤，并在低至115°C的温度下激活了NO与CO的协同反应。这项工作可以指导高性能催化剂的开发，采用高阶轨道杂化策略并结合串联概念，以实现多功能催化应用。
