Samples of well-controlled nanoparticles consisting of alloys of cobalt and nickel of different atomic ratios were synthesized using wet chemical methods with oleylamine as the solvent and the reducing agent. These materials were characterized by a variety of techniques, including high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). Small amounts of heterogenized catalysts were prepared using alumina as the support. However, the potential for use of Co–Ni catalysts in CO hydrogenation was explored using a larger amount of Co–Ni/alumina catalyst prepared from standard aqueous impregnation methods and tested in a continuously stirred tank reactor (CSTR) for Fischer–Tropsch synthesis (FTS). Results are compared to a reference catalyst containing only cobalt. The heterogenized catalysts were characterized using synchrotron methods, including temperature programmed reduction with extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge spectroscopy (TPR-EXAFS/XANES). The characterization results support intimate contact between Co and Ni, strongly suggesting alloy formation. In FTS testing, drawbacks of Ni addition included decreased CO conversion on a per gram catalyst basis, although Ni did not significantly impact the turnover number of cobalt, and produced slightly higher light gas selectivity. Benefits of Ni addition included an inverted induction period relative to undoped Co/Al2O3, where CO conversion increased with time on-stream in the initial period, and the stabilization of cobalt nanoparticles at a lower weight % of Co.

The effect of cobalt substitution with nickel was investigated for the Fischer–Tropsch synthesis reaction. Catalysts having different Ni/Co ratios were prepared by aqueous incipient wetness co-impregnation, characterized, and tested using a continuously stirred tank reactor (CSTR) for more than 200 h. The addition of nickel did not significantly modify the morphological properties measured. XRD, STEM, and TPR-XANES results showed intimate contact between nickel and cobalt, strongly suggesting the formation of a Co-Ni solid oxide solution in each case. Moreover, TPR-XANES indicated that nickel addition improves the cobalt reducibility. This may be due to H2 dissociation and spillover, but is more likely the results of a chemical effect of intimate contact between Co and Ni resulting in Co-Ni alloying after activation. FTS testing revealed a lower initial activity when nickel was added. However, CO conversion continuously increased with time on-stream until a steady-state value (34%–37% depending on Ni/Co ratio) was achieved, which was very close to the value observed for undoped Co/Al2O3. This trend suggests nickel can stabilize cobalt nanoparticles even at a lower weight percentage of Co. Currently, the cobalt price is 2.13 times the price of nickel. Thus, comparing the activity/price, the catalyst with a Ni/Co ratio of 25/75 has better performance than the unpromoted catalyst. Finally, nickel-promoted catalysts exhibited slightly higher initial selectivity for light hydrocarbons, but this difference typically diminished with time on-stream; once leveling off in conversion was achieved, the C5+ selectivities were similar (≈ 80%) for Ni/Co ratios up to 10/90, and only slightly lower (≈ 77%) at Ni/Co of 25/75.