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

Abstract

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.