@article{Li2026, 
author = {Dongpo Li and Chao Xiong and Qianqian Mao and Luying Xi and Tianfu Yang and Peng Hu and Hongbing Ji},
title = {Boosting cumene hydrogen transfer via a Ru-based porphyrin covalent organic framework for tandem air epoxidation of olefins},
year = {2026},
journal = {Nano Research},
volume = {19},
number = {1},
pages = {94907892},
keywords = {tandem catalysis, porphyrin covalent organic framework, dehydrogenation enhancement, air oxidation, inert olefins},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94907892},
doi = {10.26599/NR.2025.94907892},
abstract = {Constructing catalysts featuring an ordered structure, stable performance, and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins. Here, we design catalysts by tracing the oxidation-process origin and synthesize a series of highly dispersed metal porphyrin-based covalent organic frameworks (COFs) materials. The aim is to efficiently oxidize the C–H bonds of cumene by air to in-situ generate organic peroxides at a safe concentration, and integrate the multi-step oxidation method of cumene in industry into a one-step method for olefins’ epoxidation. The carbonyl-ruthenium COF (Ru-COF-1) exhibits excellent performance, with 98% epoxide selectivity, 1221.77 h−1 productivity, and over 95% selectivity after 9 cycles for 1-hexene. Analysis of structure–properties–catalytic relationships of Ru-COF-1 shows that, compared with Ru-porphyrins and metal-free COFs, the enhanced reaction performance mainly results from Ru metal introduction, which promotes benzylic proton transfer in cumene. Besides, Ru-COF-1’s porous, ordered structure aids oxygen enrichment, forming active peroxy radicals with the cumene carbon-centered radicals formed on the catalyst surface. Ru-H sites then accelerate active oxygen transfer from peroxy radicals, enabling olefin tandem epoxidation. Density functional theory (DFT) calculations verify the reaction mechanism, and this work offers a reference for the design of catalysts for the green, safe, and efficient oxidation of olefins.}
}