Operando Electron Microscopy Study of Cobalt-Based Fischer-Tropsch Nanocatalysts

Kassiogé Dembélé (1, 2) , Mounib Bahri (1) , Charles Hirlimann (1) , Simona Moldovan (1) , Adrien Berliet (2) , Sylvie Maury (2) , Anne‐sophie Gay (2) , Ovidiu Ersen (1, 3)

1 IPCMS - Institut de Physique et Chimie des Matériaux de Strasbourg
2 IFPEN - IFP Energies nouvelles
3 IUF - Institut universitaire de France

Thanks to their stability and selectivity for long-chains hydrocarbons, supported Co nanoparticles are the most commonly used catalysts in the Fischer-Tropsch synthesis reaction. We report here on the use of in situ transmission electron microscopy (TEM) to address the real-time evolution of cobalt-based catalysts during their reduction under relevant industrial activation condition (105 Pa, 430 °C), and their operation in syngas (H2/CO=2, 105 Pa, 220 °C). To do so, we chose Co3O4−Pt nanoparticles supported on silica or alumina that can be directly compared to some industrial catalysts. By analysing the real space information contained in the TEM images, we have monitored the fragmentation of cobalt aggregates, the disappearance of cavities within the particles, their shape changes, the particle diffusion and coalescence processes, as well as the effect of the support (silica or alumina) on the behaviour of the Co phase. An easier reduction of cobalt catalysts supported on silica as compared to the same catalyst supported on alumina was also observed. During the catalyst operation under syngas, we have noticed the stability of the general shape of the particles. Simultaneously, using a residual gas analyser connected to the TEM holder, the main gas products of the Fischer-Tropsch reaction were systematically analysed. Our findings underline the benefit of the operando TEM to study the dynamical evolution of catalysts, at the nanoparticle level, under operation conditions.

Mots clés: in situ TEM; cobalt-based catalysts; reduction; syngas conversion; Fischer-Tropsch synthesis; operando study

Domaines: Chimie

Kassiogé Dembélé, Mounib Bahri, Charles Hirlimann, Simona Moldovan, Adrien Berliet, et al.. Operando Electron Microscopy Study of Cobalt-Based Fischer-Tropsch Nanocatalysts. ChemCatChem, 2021, 13 (8), pp.1920-1930. ⟨10.1002/cctc.202001074⟩. ⟨hal-03274934⟩