Iron and Copper Nanoparticles Inside and Outside Carbon Nanotubes: Nanoconfinement, Migration, Interaction and Catalytic Performance in Fischer-Tropsch Synthesis

Abstract Carbon materials have attracted increasing attention as supports for metal catalysts. Iron-containing carbon nanotubes often promoted with copper have found application in Fischer-Tropsch synthesis, which provides an alternative way for conversion of renewable feedstocks to chemicals and fuels. In carbon nanotubes, the active phase can be nanoconfined inside the channels or localized on the outer surface. In most of previous work, the distribution of metal nanoparticles inside or outside carbon nanotubes is considered to be immobile during the catalyst activation or catalytic reaction. In this paper, we uncovered remarkable mobility of both iron and copper species in the bimetallic catalysts between inner carbon nanotube channels and outer surface, which occurs in carbon monoxide and syngas, while almost no migration of iron species proceeds in the monometallic catalysts. This mobility is enhanced by noticeable fragility and defects in carbon nanotubes, which appear on their impregnation with the acid solutions of metal precursors and precursor decomposition. Remarkable mobility of iron and copper species in bimetallic catalysts affects the genesis of iron active sites, and enhances interaction of iron with the promoter. In the bimetallic iron-copper catalysts, the major increase in the activity was attributed to higher reaction turnover frequency over iron surface sites located in a close proximity with copper.