Stabilizing the active phase of iron-based Fischer–Tropsch catalysts for lower olefins: mechanism and strategy

摘要

Fischer–Tropsch synthesis of lower olefins (FTO) is a classical yet modern topic of great significance in which the supported Fe-based nanoparticles are the most promising catalysts. The performance deterioration of catalysts is a big challenge due to the instability of the nanosized active phase of iron carbides. Herein, by in situ mass spectrometry, theoretical analysis, and atmospheric- and high-pressure experimental examinations, we revealed the Ostwald-ripening-like growth mechanism of the active phase of iron carbides in FTO, which involves the cyclic formation–decomposition of iron carbonyl intermediates to transport iron species from small particles to large ones. Accordingly, by suppressing the formation of iron carbonyl species with a high-N-content carbon support, the size and structure of the active phase were regulated and stabilized, and durable iron-based catalysts were conveniently obtained with the highest selectivity for lower olefins up to 54.1%. This study provides a practical strategy for exploring advanced FTO catalysts.