As an important class of versatile organic compounds and reactive intermediates, epoxides are widely used in pharmaceuticals, pesticides, coatings, and other fields. They have high chemical activity and can be further converted into other high-value chemicals. Thus, the large-scale application and the huge market demands have attracted significant attention from numerous enterprises and research institutions.
A team of light hydrocarbon conversion led by Hongbing Ji from Zhejiang University of technology in Hangzhou, China recently outlined the state of light olefin epoxidation technology to advance research in the field. It is of great significance to select appropriate porphyrin skeletons and metal active centers to achieve uniform dispersion and stable loading of metals, and to construct a catalytic system for the in-situ activation of alkyl C-H bonds to generate peroxy species and realize the tandem epoxidation of inert olefins. The research devises a safe, simple, environmentally-friendly and cost-effective synergetic-tandem catalysis strategy for the epoxidation of olefins by air, as well as a method for preparing catalysts with outstanding epoxidation capabilities. This work has important reference value for subsequent industrial transformation and application.
The team published their review in Nano Research on December 30, 2025.
At present, there are several main production processes of epoxides including chlorohydrin, co-oxidation, and direct oxidation. However, the preparation of epoxides by these processes usually requires either the use of chlorine and a strong base or epoxidation with peracids and hydrogen peroxide, and these methods are always constrained by many issues such as environmental pollution, safety hazards, and low reaction performance.
Alkyl hydroperoxides, including tert-butyl hydroperoxide (THPB), ethylbenzene hydroperoxide (EBHP) and cumene hydroperoxide (CHP), have been increasingly valued due to their environmentally friendly characteristics and the high economic value of by-products in the epoxidation reaction. However, the production process of alkyl hydroperoxides from isobutane, ethylbenzene or cumene still faces many issues such as a large number of co-products, equipment corrosion, complex processing and strict operating conditions. Also, the storage and transportation of high-concentration alkyl hydrogen peroxides are difficult and unsafe, and they also have certain limitations as they are highly reactive and thus prone to self-decomposition. Therefore, the epoxidation of olefins by the in-situ generation of safe concentration of alkyl peroxide in the reaction system is a significant strategy. However, the development of a “one-pot” catalytic system to effectively activate the C-H bonds of isobutane, ethylbenzene or cumene to in-situ generate alkyl peroxide for enhancing the selectivity of epoxides still faces plenty of challenges.
Based on all the above considerations, the work has developed a synergetic-tandem strategy to construct a metal porphyrin-based COF catalyst for the epoxidation of inert olefines using air as the oxidant to prepare high-value epoxides. In an air atmosphere, the catalyst (Ru-COF-1) can efficiently activate the benzylic C-H bond of cumene, in-situ generating peroxy species. Additionally, it is capable of effectively regulating the selective transfer of active oxygen, thereby enabling the tandem epoxidation of light olefins represented by 1-hexene.
Other contributors include, Dongpo Li, Chao Xiong, Qianian Mao, Luying Xi and Peng Hu from State Key Laboratory of Green Chemical Synthesis and Conversion, Institute of Green Petroleum Processing and Light Hydrocarbon Conversion, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, China and Tianfu Yang at Guangxi University in Nanning, China.
This work was financially supported by the National Key Research and Development Program Nanotechnology Specific Project (No.2020YFA0210900), National Natural Science Foundation of China (No. 21938001), Science and Technology Planning Project of Guangdong Province (STKJ2023015), Natural Science Foundation of Guangdong Province (2023B1515020101), Innovative Team Project of Guangdong Ordinary University (2019KCXTD002)
About Nano Research
Nano Research is a peer-reviewed, open access, international and interdisciplinary research journal, sponsored by Tsinghua University and the Chinese Chemical Society, published by Tsinghua University Press on the platform SciOpen. It publishes original high-quality research and significant review articles on all aspects of nanoscience and nanotechnology, ranging from basic aspects of the science of nanoscale materials to practical applications of such materials. After 18 years of development, it has become one of the most influential academic journals in the nano field. Nano Research has published more than 1,000 papers every year from 2022, with its cumulative count surpassing 7,000 articles. In 2024 InCites Journal Citation Reports, its 2024 IF is 9.0 (8.7, 5 years), and it continues to be the Q1 area among the four subject classifications. Nano Research Award, established by Nano Research together with TUP and Springer Nature in 2013, and Nano Research Young Innovators (NR45) Awards, established by Nano Research in 2018, have become international academic awards with global influence.
Nano Research
Boosting cumene hydrogen transfer via a Ru-based porphyrin covalent organic framework for tandem air epoxidation of olefins
30-Dec-2025