Boosting the epoxidation of long-chain linear α-olefins via bimetallic CoIr composite

Abstract

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. • 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.