The nanoscale distribution of the supported metal phase is an important property for highly active, selective, and stable catalysts. Here, the nanoscale redistribution and aggregate formation of cobalt nitrate during the synthesis of supported cobalt catalysts were studied. Drying over a range of temperatures in stagnant air resulted in cobalt particles (8 nm) present in large aggregates (30–150 nm). However, drying in a N2 flow resulted in cobalt nanoparticles distributed either in aggregates or uniformly on various SiO2 and γ-Al2O3 supports, critically dependent on the drying temperature. The mechanism of aggregation was studied through chemical immobilization of the precursor on a silica support after drying in a N2 flow. The aggregation behavior upon drying in a gas flow at temperatures below 100 °C showed a remarkable similarity to distributions obtained upon the dewetting of colloidal films, suggesting a physical process. Alternatively, by inducing decomposition of the cobalt nitrate above 100 °C before drying was complete, aggregation was brought about through a chemical process that occurred both in stagnant and flowing gas. A γ-alumina support exhibited increased precursor-support interactions and displayed little cobalt aggregation upon drying in a gas flow but extensive aggregation upon drying in stagnant air. The aggregation behavior was further tested on silica supports with pore sizes between 3 and 15 nm and tested under industrially relevant Fischer–Tropsch conditions, which revealed that uniform cobalt nanoparticle distributions were up to 50% more active compared to aggregated systems. Thus, hydrodynamics and the temperature of the gas phase are critical parameters to control nanoscale distributions during drying of functional nanomaterials such as supported catalysts.

Ordered mesoporous carbon (CMK‐3) with different surface modifications is applied as a support for Fe‐based catalysts in the Fischer–Tropsch to olefins synthesis (FTO) with and without sodium and sulfur promoters. Different concentrations of functional groups do not affect the size (3–5 nm) of Fe particles in the fresh catalysts but iron (carbide) supported on N‐enriched CMK‐3 and a support with a lower concentration of functional groups show higher catalytic activity under industrially relevant FTO conditions (340 °C, 10 bar, H2/CO=2) compared to a support with an O‐enriched surface. The addition of promoters leads to more noticeable enhancements of the catalytic activity (3–5 times higher) and the selectivity to C2–C4 olefins (≈2 times higher) than surface functionalization of the support. Nitrogen surface functionalization and removal of surface groups before impregnation and calcination, however, further increase the activity of the catalysts in the presence of promoters. The confinement of the Fe nanoparticles in the mesopores of CMK‐3 restricts but does not fully prevent particle growth and, consequently, the decrease of activity under FTO conditions.

No abstract

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters.

Colloidal synthesis of nanocrystals (NC) followed by their attachment to a support and activation is a promising route to prepare model catalysts for research on structure-performance relationships. Here, we investigated the suitability of this method to prepare well-defined Co/TiO2 and Co/SiO2 catalysts for the Fischer–Tropsch (FT) synthesis with high control over the cobalt particle size. To this end, Co-NC of 3, 6, 9, and 12 nm with narrow size distributions were synthesized and attached uniformly on either TiO2 or SiO2 supports with comparable morphology and Co loadings of 2–10 wt %. After activation in H2, the FT activity of the TiO2-supported 6 and 12 nm Co-NC was similar to that of a Co/TiO2 catalyst prepared by impregnation, showing that full activation was achieved and relevant catalysts had been obtained; however, 3 nm Co-NC on TiO2 were less active than anticipated. Analysis after FT revealed that all Co-NC on TiO2 as well as 3 nm Co-NC on SiO2 had grown to ∼13 nm, while the sizes of the 6 and 9 nm Co-NC on SiO2 had remained stable. It was found that the 3 nm Co-NC on TiO2 already grew to 10 nm during activation in H2. Furthermore, substantial amounts of Co (up to 60%) migrated from the Co-NC to the support during activation on TiO2 against only 15% on SiO2. We showed that the stronger interaction between cobalt and TiO2 leads to enhanced catalyst restructuring as compared to SiO2. These findings demonstrate the potential of the NC-based method to produce relevant model catalysts to investigate phenomena that could not be studied using conventionally synthesized catalysts.