Ma Dingren, Lian Qiyu, Zhang Yexing, Huang Yajing, Guan Xinyi, Liang Qiwen, He Chun, Xia Dehua, Liu Shengwei, Yu Jiaguo
School of Environmental Science and Engineering, Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Sun Yat-sen University, Guangzhou, 510275, China.
Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan, 430078, China.
Nat Commun. 2023 Nov 2;14(1):7011. doi: 10.1038/s41467-023-42853-8.
The structure-activity relationship in catalytic ozonation remains unclear, hindering the understanding of activity origins. Here, we report activity trends in catalytic ozonation using a series of single-atom catalysts with well-defined M-NC (M: manganese, ferrum, cobalt, and nickel) active sites. The M-NC units induce locally polarized M - C bonds to capture ozone molecules onto M atoms and serve as electron shuttles for catalytic ozonation, exhibiting excellent catalytic activities (at least 527 times higher than commercial manganese dioxide). The combined in situ characterization and theoretical calculations reveal single metal atom-dependent catalytic activity, with surface atomic oxygen reactivity identified as a descriptor for the structure-activity relationship in catalytic ozonation. Additionally, the dissociation barrier of surface peroxide species is proposed as a descriptor for the structure-activity relationship in ozone decomposition. These findings provide guidelines for designing high-performance catalytic ozonation catalysts and enhance the atomic-level mechanistic understanding of the integral control of ozone and methyl mercaptan.
催化臭氧化反应中的构效关系仍不明确，这阻碍了对活性起源的理解。在此，我们报告了使用一系列具有明确M-NC（M：锰、铁、钴和镍）活性位点的单原子催化剂进行催化臭氧化反应的活性趋势。M-NC单元诱导局部极化的M-C键，将臭氧分子捕获到M原子上，并作为催化臭氧化反应的电子穿梭体，表现出优异的催化活性（至少比商业二氧化锰高527倍）。结合原位表征和理论计算揭示了单金属原子依赖性催化活性，表面原子氧反应性被确定为催化臭氧化反应中构效关系的描述符。此外，还提出表面过氧化物物种的解离势垒作为臭氧分解中构效关系的描述符。这些发现为设计高性能催化臭氧化催化剂提供了指导，并增强了对臭氧和甲硫醇整体控制的原子水平机理理解。
