Synthesis and Characterization of Supported Cobalt–Manganese Nanoparticles as Model Catalysts for Fischer–Tropsch Synthesis

Abstract Supported Co is an effective catalyst for the Fischer–Tropsch synthesis of various hydrocarbon products that can be converted to diesel. Recent studies have shown that the formation of methane can be suppressed and the formation of C 5+ products enhanced by promoting Co with Mn. Because the activity and product selectivity of Co‐based catalysts are dependent on the size of Co nanoparticles and the extent of Co promotion by Mn, it is desirable to understand these effects by investigating the performance of Co nanoparticles with well‐defined size and elemental composition. The present study was undertaken with the aim of producing well‐defined nanoparticles of Co and Co–Mn and then supporting them on silica. Co and Co–Mn particles were synthesized through the polyol reduction of Co and Mn acetylacetonates. By controlling synthesis conditions, Co particles with diameters of 7–10 nm and similarly sized Co–Mn (Mn/Co=0.1) particles were prepared. XRD and elemental mapping with scanning TEM‐energy‐dispersive X‐ray spectroscopy and scanning TEM‐electron energy loss spectroscopy studies suggested that most of the Mn species was associated with the Co particles. Ex situ prepared Co and Co–Mn nanoparticles were first supported on silica and then investigated for the catalytic activity for the Fischer–Tropsch synthesis. The turnover frequencies and product distributions obtained with silica‐supported Co and Co–Mn nanoparticles were similar to those obtained with catalysts prepared by using the conventional incipient wetness impregnation method. However, the rate of CO consumption per mass of Co was much lower for the catalysts produced by supporting ex situ prepared nanoparticles. This effect was attributed to the sintering of the nanoparticles during their calcination and reduction. Magnetic interactions among nanoparticles during their immobilization and thermal pretreatment were identified as the primary cause of sintering.