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

• DOI: 10.1073/pnas.2319119121
• Publication Date: 2024-04-08T19:00:46Z
• Authors: Wei Qu; Zhuoyun Tang; Su Tang; Tao Zhong; Huinan Zhao; Shuanghong Tian; Dong Shu; Chun He
• Keywords: Antibonding molecular orbital; Bond cleavage

The advancement of atomically precise dinuclear heterogeneous catalysts holds great potential in achieving efficient catalytic ozonation performance and contributes to the understanding synergy mechanisms during reaction conditions. Herein, we demonstrate a “ship-in-a-bottle pyrolysis” strategy that utilizes Fe 2 (CO) 9 dinuclear-cluster precisely construct site, consisting two 1 -N 3 units connected by Fe-Fe bonds firmly bonded N-doped carbon. Systematic characterizations theoretical modeling reveal coordination motif markedly reduced devotion antibonding state Fe-O bond because strong orbital coupling interaction dual d - orbitals. This facilitates O-O covalent cleavage O enhances binding strength with intermediates (atomic oxygen species; *O *OO), thus boosting performance. As result, site catalyst exhibits 100% efficiency for CH SH elimination, outperforming commercial MnO 1,200-fold. research provides insights into atomic-level structure–activity relationship extends use beyond.