Subsurface Single‐Atom Catalyst Enabled by Mechanochemical Synthesis for Oxidation Chemistry

• Published in: Angewandte Chemie Vol. 136; no. 42
• Main Authors: Guan, Xuze, Han, Rong, Asakura, Hiroyuki, Wang, Bolun, Chen, Lu, Yan, Jay Hon Cheung, Guan, Shaoliang, Keenan, Luke, Hayama, Shusaku, Spronsen, Matthijs A., Held, Georg, Zhang, Jie, Gu, Hao, Ren, Yifei, Zhang, Lun, Yao, Zhangyi, Zhu, Yujiang, Regoutz, Anna, Tanaka, Tsunehiro, Guo, Yuzheng, Wang, Feng Ryan
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 14.10.2024
• Subjects: Adsorption; ammonia oxidation; ball milling; Catalysts; Chemical synthesis; Ferric oxide; heterogeneous catalysis; Oxidation; Poisoning (reaction inhibition); Reaction mechanisms; single-atom catalysts; Sintering; surface chemistry
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202410457

Single‐atom catalysts have garnered significant attention due to their exceptional atom utilization and unique properties. However, the practical application of these catalysts is often impeded by challenges such as sintering‐induced instability and poisoning of isolated atoms due to strong gas adsorption. In this study, we employed the mechanochemical method to insert single Cu atoms into the subsurface of Fe2O3 support. By manipulating the location of single atoms at the surface or subsurface, catalysts with distinct adsorption properties and reaction mechanisms can be achieved. It was observed that the subsurface Cu single atoms in Fe2O3 remained isolated under both oxidation and reduction environments, whereas surface Cu single atoms on Fe2O3 experienced sintering under reduction conditions. The unique properties of these subsurface single‐atom catalysts call for innovations and new understandings in catalyst design. The mechanochemical approach has been shown to be an effective method of regulating the position of single atoms. Controlling single atoms at the surface or subsurface results in catalysts with very different adsorption properties, leading to different reaction mechanisms. As a result, the subsurface Cu single‐atom catalyst shifts the conversion profile 80 K towards the low‐temperature region and NH3 is completely converted at 513 K.