Disk-Shaped Cobalt Nanocrystals as Fischer–Tropsch Synthesis Catalysts Under Industrially Relevant Conditions

Abstract

Colloidal synthesis of metal nanocrystals (NC) offers control over size, crystal structure and shape of nanoparticles, making it a promising method to synthesize model catalysts to investigate structure-performance relationships. Here, we investigated the synthesis of disk-shaped Co-NC, their deposition on a support and performance in the Fischer–Tropsch (FT) synthesis under industrially relevant conditions. From the NC synthesis, either spheres only or a mixture of disk-shaped and spherical Co-NC was obtained. The disks had an average diameter of 15 nm, a thickness of 4 nm and consisted of hcp Co exposing (0001) on the base planes. The spheres were 11 nm on average and consisted of ε-Co. After mild oxidation, the CoO-NC were deposited on SiO2 with numerically 66% of the NC being disk-shaped. After reduction, the catalyst with spherical plus disk-shaped Co-NC had 50% lower intrinsic activity for FT synthesis (20 bar, 220 °C, H2/CO = 2 v/v) than the catalyst with spherical NC only, while C5+-selectivity was similar. Surprisingly, the Co-NC morphology was unchanged after catalysis. Using XPS it was established that nitrogen-containing ligands were largely removed and in situ XRD revealed that both catalysts consisted of 65% hcp Co and 21 or 32% fcc Co during FT. Furthermore, 3–5 nm polycrystalline domains were observed. Through exclusion of several phenomena, we tentatively conclude that the high fraction of (0001) facets in disk-shaped Co-NC decrease FT activity and, although very challenging to pursue, that metal nanoparticle shape effects can be studied at industrially relevant conditions.