In situ reduction study of cobalt model Fischer-Tropsch synthesis catalysts.

Fischer-Tropsch (FT) synthesis is an important process to manufacture hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The catalysis process occurs on, for example, cobalt metal surfaces at elevated temperatures and pressures. A fundamental understanding of the reduction pathway of supported cobalt oxides, and the intermediate species present during the activation, can assist in developing improved industrial supported cobalt catalysts. Hard synchrotron X-rays have the unique ability to probe atomic processes both in terms of phases present as well as the crystallographic and local structure (using the pair distribution function approach) under realistic conditions. In this manuscript we present results from measurements during in situ hydrogen activation of a model Co/alumina catalyst using in situ synchrotron X-ray powder diffraction and pair-distribution function (PDF) analysis on beam line ID31 at the ESRF in Grenoble, France. The PDF analysis showed a substantially improved understanding of the reduction of cobalt oxides, as for the first time all cobalt could be accounted for by using total scattering analysis.

Rietveld and pair distribution function study of Hägg carbide using synchrotron X-ray diffraction.

Fischer-Tropsch (FT) synthesis is an important process in the manufacturing of hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The reduced iron catalyst reacts with carbon monoxide and hydrogen to form bulk Fe(5)C(2) Hägg carbide (χ-HC) during FT synthesis. Arguably, χ-HC is the predominant catalyst phase present in the working iron catalyst. Deactivation of the working catalyst can be due to oxidation of χ-HC to iron oxide, a step-wise decarburization to cementite (θ-Fe(3)C), carbon formation or sintering with accompanying loss of catalytic performance. It is therefore critical to determine the precise crystal structure of χ-HC for the understanding of the synthesis process and for comparison with the first-principles ab initio modelling. Here the results of high-resolution synchrotron X-ray powder diffraction data are reported. The atomic arrangement of χ-HC was confirmed by Rietveld refinement and subsequent real-space modelling of the pair distribution function (PDF) obtained from direct Fourier transformation. The Rietveld and PDF results of χ-HC correspond well with that of a pseudo-monoclinic phase of space group Pi [a = 11.5661 (6) Å, b = 4.5709 (1) Å, c = 5.0611 (2) Å, α = 89.990 (5)°, ß = 97.753 (4)°, γ = 90.195 (4)°], where the Fe atoms are located in three distorted prismatic trigonal and one octahedral arrangement around the central C atoms. The Fe atoms are distorted from the prismatic trigonal arrangement in the monoclinic structure by the change in C atom location in the structure.