Precisely constructing orbital coupling- modulated iron dinuclear site for enhanced catalytic ozonation performance

• 成果类型: Article
• 署名作者: Qu, Wei; Tang, Zhuoyun; Tang, Su; Zhong, Tao; Zhao, Huinan; Tian, Shuanghong; Shu, Dong; He, Chun
• 署名单位: Sun Yat Sen University; South China Normal University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-15396
• DOI: 10.1073/pnas.2319119121
• 发表日期: 2024-04-16

摘要

The advancement of atomically precise dinuclear heterogeneous catalysts holds great potential in achieving efficient catalytic ozonation performance and contributes to the understanding of synergy mechanisms during reaction conditions. Herein, we demonstrate a ship - in - a- bottle and pyrolysis strategy that utilizes Fe2(CO)9 dinuclear- cluster to precisely construct Fe2 site, consisting of two Fe1-N3 units connected by Fe - Fe bonds and firmly bonded to N - doped carbon. Systematic characterizations and theoretical modeling reveal that the Fe - Fe coordination motif markedly reduced the devotion of the antibonding state in the Fe - O bond because of the strong orbital coupling interaction of dual Fe d - d orbitals. This facilitates O - O covalent bond cleavage of O3 and enhances binding strength with reaction intermediates (atomic oxygen species; *O and *OO), thus boosting catalytic ozonation performance. As a result, Fe dinuclear site catalyst exhibits 100% ozonation efficiency for CH3SH elimination, outperforming commercial MnO2 catalysts by 1,200 - fold. This research provides insights into the atomiclevel structure-activity relationship of ozonation catalysts and extends the use of dinuclear catalysts in catalytic ozonation and beyond.