Developing catalysts for the selective oxidation of alkenes with environment‐friendly, unique structural characteristics, high economic benefit and better catalytic performance is important. Herein, we employed ZIF‐67 as the sacrificial template to synthesize bimetallic‐organic frameworks CoxMo100‐x‐ZIF nanocages by a facile dissolution‐regrowth strategy. The Co51.8Mo48.2‐ZIF catalyst was tested under various experimental parameters for the selective oxidation of cyclooctene to screen the optimal reaction conditions. Under the optimal reaction conditions, Co51.8Mo48.2‐ZIF nanocages exhibited a high cyclooctene conversion of 99.3 % and a selectivity of 99.0 % to epoxy cyclooctane. Furthermore, Co51.8Mo48.2‐ZIF nanocages can maintain their catalytic performance after reused five catalytic cycles. This bimetallic catalyst could also be used for the epoxidation of a wide range of alkenes, such as hexene or cyclohexene. In addition, the kinetic studies were conducted, and a reasonable reaction mechanism was proposed based on density functional theory calculations. The outstanding catalytic performance of CoxMo100‐x‐ZIF nanocages can be attributed to the cooperativity between Co and Mo sites and the hollow structure with high surface areas.

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An eco-friendly strategy for the synthesis of highly ordered meso-and microporous zeolites is required both in academia and industry. Therefore, asymmetrical anionic-nonionic gemini surfactants, polyoxyethylene laurinol ether sodium sulfoitaconate (Gemini-n), have been designed, synthesized and used in the directed synthesis of hierarchical ZSM-5 zeolites (HZSM-5) by imparting substantial mesoporosity. The hydrothermal temperature, the amount of gemini surfactants and the crystallization time strongly affected the crystallization degree and the textural properties of the HZSM-5. The tune of the porous size distribution (microporous to mesoporous) can be obtained by varying the number of the ethylene oxide units in the gemini surfactants. Besides, the use of these novel anionicnonionic gemini surfactants is an effective strategy to avoid phase-separation. The existence of abundant hydroxyl groups on the surface of HZSM-5 was used to immobilize molybdenum compound by the stable MoÀ O bond. The complex with abundant intercrystal mesopores exhibited superior catalytic performance with high yield and selectivity for the epoxidation reactions of alkenes as compared to the conventional ZSM-5. Moreover, the complex presented high catalytic ability after been reused for five times.

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