An Investigation into the Effects of Mn Promotion on the Activity and Selectivity of Co/SiO2 for Fischer鈥揟ropsch Synthesis: Evidence for Enhanced CO Adsorption and Dissociation

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• 作者：Gregory R. Johnson ; Sebastian Werner ; Alexis T. Bell
• 刊名：ACS Catalysis
• 出版年：2015
• 出版时间：October 2, 2015
• 年：2015
• 卷：5
• 期：10
• 页码：5888-5903
• 全文大小：789K
• ISSN：2155-5435

文摘

Mn is an effective promoter for improving the activity and selectivity of Co-based Fischer鈥揟ropsch synthesis (FTS) catalysts, but the mechanism by which this promoter functions is poorly understood. The work reported here was aimed at defining the manner in which Mn interacts with Co and determining how these interactions affect the activity and selectivity of Co. Detailed measurements are reported for the kinetics of FTS as a function of Mn/Co ratio, temperature, and reactant partial pressure. These data are described by a single, two-parameter rate expression. Mn promotion was found to increase both the apparent rate constant for CO consumption and the CO adsorption constant. Further evidence for enhanced CO adsorption and dissociation was obtained from measurements of temperature-programmed desorption of CO and CO disproportionation rates, respectively. Quantitative analysis of elemental maps obtained by STEM-EDS revealed that the promoter accumulates preferentially on the surface of Co nanoparticles at low Mn loadings, resulting in a rapid onset of improvements in the product selectivity as the Mn loading increases. For catalysts prepared with loadings higher than Mn/Co = 0.1, the additional Mn accumulates in the form of nanometer-scale particles of MnO on the support. In situ IR spectra of adsorbed CO show that Mn promotion increases the abundance of adsorbed CO with weakened C鈥揙 bonds. It is proposed that the cleavage of the C鈥揙 bond is promoted through Lewis acid鈥揵ase interactions between the Mn²⁺ cations located at the edges of MnO islands covering the Co nanoparticles and the O atom of CO adsorbates adjacent to the MnO islands. The observed decrease in selectivity to CH₄ and the increased selectivity to C₅₊ products with increasing Mn/Co ratio are attributed to a decrease in the ratio of adsorbed H to CO on the surface of the supported Co nanoparticles.