Regulating the electronic structure through charge redistribution in dense single-atom catalysts for enhanced alkene epoxidation

• Published in: Nature communications Vol. 14; no. 1; pp. 2494 - 10
• Main Authors: Jin, Hongqiang, Zhou, Kaixin, Zhang, Ruoxi, Cui, Hongjie, Yu, Yu, Cui, Peixin, Song, Weiguo, Cao, Changyan
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 29.04.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 140/133; 140/146; 147/135; 147/137; 147/143; 639/301/299/1013; 639/638/77/884; 639/638/77/887; Alkenes; Catalysts; Chemical synthesis; Cobalt; Electronic structure; Epoxidation; Humanities and Social Sciences; Laboratories; Microscopy; multidisciplinary; Population density; Science; Science (multidisciplinary); Single atom catalysts; Soil sciences; Stilbene; trans-Stilbene; Wavelet transforms
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-38310-1

Inter-site interaction in densely populated single-atom catalysts has been demonstrated to have a crucial role in regulating the electronic structure of metal atoms, and consequently their catalytic performances. We herein report a general and facile strategy for the synthesis of several densely populated single-atom catalysts. Taking cobalt as an example, we further produce a series of Co single-atom catalysts with varying loadings to investigate the influence of density on regulating the electronic structure and catalytic performance in alkene epoxidation with O 2 . Interestingly, the turnover frequency and mass-specific activity are significantly enhanced by 10 times and 30 times with increasing Co loading from 5.4 wt% to 21.2 wt% in trans-stilbene epoxidation, respectively. Further theoretical studies reveal that the electronic structure of densely populated Co atoms is altered through charge redistribution, resulting in less Bader charger and higher d-band center, which are demonstrated to be more beneficial for the activation of O 2 and trans-stilbene. The present study demonstrates a new finding about the site interaction in densely populated single-atom catalysts, shedding insight on how density affects the electronic structure and catalytic performance for alkene epoxidation. The interaction among single sites in densely populated single-atom catalysts (SACs) has received much attention. Here the authors report a general and facile strategy for the synthesis of several densely populated SACs and decipher the influence of density on regulating their electronic structure and catalytic performance in alkene epoxidation.