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We demonstrate our strategy by constructing copper metal sites with appropriate electronic density via exploiting the metal-support interaction, to improve the yield of epoxides in the epoxidation of long-chain LAOs. We anticipate that the proposed strategy would enrich the current comprehension of the heterogeneous epoxidation process and affords feasible valorization of olefins in the FTS crudes. [Display omitted] • The supported copper catalysts with high dispersion and uniform size distribution were prepared via chemisorption-hydrolysis technique. • The electronic density of the copper sites is modulated by the metal-support interaction. • The CuO/Al2O3 catalyst exhibits near 100% yield in production of 1,2-epoxydecane. • Our strategy greatly holds great potential for the valorization of FTS crude. Catalytic epoxidation of linear α-olefins (LAOs) through Mukaiyama epoxidation provides a premier route to valorization of these unique valuable materials in the Fischer-Tropsch synthesis crude. However, this reaction suffers a kinetically slow formation of key acyl/acyl peroxy radicals by the metal-based catalysts when using O 2 as oxidant, resulting in the lowered overall reaction efficiency. Herein, we report a strategy for rational tuning the electronic properties of transition metal oxides catalyst by modulation of metal-support interaction, which could realize almost perfect yield (99%) of desired epoxides in transformation of 1-decene. Varieties of experimental and theoretical characterizations demonstrate that the superior catalytic performance results from the altered electronic state of active sites, which is closely correlated with the electronic interaction between metal oxide and support. This work greatly advances catalytic epoxidation of long-chain LAOs and paves the road for valorization of FTS crude. [ABSTRACT FROM AUTHOR]

We report a novel approach to prepare a bimetallic CoIr composite catalyst and it exhibits an unrivaled space-time yield in production of 1,2-epoxydecane, approximately 6 times to that state-of-the-art Co-based precedent. This strategy also shows excellent compatibility to extended substrate scope and promising future in valorization of Fischer-Tropsch synthesis crude. [Display omitted] • The bimetallic CoIr composite catalyst was prepared via pyrolysis of molecularly defined "Co-Ir" pair complex pre-catalyst. • The CoIr composite catalyst exhibited an unrivaled space-time yield, approximately 6 times to that state-of-the-art Co-based precedent. • The atomically well-dispersed electron-rich Co site could promote elementary cleavage of the "O-O" bond in the key ROO intermediate. • The CoIr composite catalyst showed excellent compatibility to extended substrate scope and promising future in valorization of Fischer-Tropsch synthesis crude. Fischer-Tropsch Synthesis (FTS) offers a premier route for mass production of industrially valuable long-chain linear α-olefins (LAOs), which cannot be directly separated for further use. Epoxidation of LAOs in FTS mixture allows for easier separation of them, however, the reaction by itself remains a substantial challenge. Herein, we prepared a Co-Ir composite via pyrolysis of molecularly defined "Co-Ir" pair complex and it exhibits an unrivaled space-time yield of 17.5 mol epo ·mol Co −1·h−1 in production of 1,2-epoxydecane, approximately 6 times to that state-of-the-art Co-based precedent. Varieties of experimental and theoretical characterizations reveal that atomically well-dispersed electron-rich Co is key in the promotion of ROO dissociation into RO. This strategy further succeeds in epoxidation of mixture containing 1-decene and n -decane, evident for its wide-range compatibility. This work greatly advances valorization of long-chain LAOs and separation of their value-added derivatives. [ABSTRACT FROM AUTHOR]