Yin, Defu, Yuan, Jiamin, Lin, Dong, Zhang, Zhihua, Fang, Wei, Liu, Zhiqiang, Yang, Chaohe, Duan, Xuezhi, Zheng, Anmin, Chen, De, Zhou, Xinggui, Wang, Liang and Feng, Xiang
2026.
Hydrophobic promoter‐enhanced tandem catalysis for alkene epoxidation with H2 and O2.
Angewandte Chemie International Edition
65
(34)
, e2551607.
10.1002/anie.2551607
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Abstract
The efficiency of tandem catalysis is fundamentally limited by the transport of transient intermediates. In the direct epoxidation of alkenes with H2 and O2, in situ generated H2O2 rapidly decomposes during diffusion, rendering most Ti active sites kinetically inaccessible and imposing a long-standing performance ceiling. Here, we overcome this limitation by engineering hydrophobic transport channels via physical integration of a hydrophobic polymer with bifunctional Au/TS-1 catalysts. This microenvironment accelerates H2O2 migration away from hydroxyl-rich surfaces toward remote Ti sites while suppressing nonproductive decomposition. Molecular dynamics simulation studies show that the diffusion of H2O2 on hydrophobic surfaces is significantly higher than on hydrophilic surfaces, as reflected experimentally by a 25% increase in tandem H2O2 efficiency. Moreover, the hydrophobic channels promote rapid desorption of epoxide products, suppressing ring-opening reactions and carbonaceous accumulation, resulting in a stable ∼90% epoxide selectivity over 200 h. This strategy exhibits broad generality across Au–Ti bifunctional catalysts for alkene epoxidation using in situ generated H2O2, with an outstanding H2 utilization efficiency of 73.5% achieved over the Au/TS-1-B catalyst under the identical standard reaction conditions employed throughout this work. This work establishes diffusion control of metastable surface species as a principle for breaking intrinsic transport–decomposition trade-offs in tandem catalysis.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI) |
| Additional Information: | RRS policy applied |
| Publisher: | Wiley |
| ISSN: | 1433-7851 |
| Date of First Compliant Deposit: | 7 July 2026 |
| Date of Acceptance: | 28 May 2026 |
| Last Modified: | 18 Aug 2026 09:45 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/187911 |
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