Study of Manganese Promoter on a Precipitated Iron-Based Catalyst for Fischer-Tropsch Synthesis

The effects of Manganese （Mn） incorporation on a precipitated iron-based Fischer-Tropsch synthesis （FTS） catalyst were investigated using N2 physical adsorption, air differential thermal analysis （DTA）, H2 temperature-programmed reduction （TPR）, and Mǒssbauer spectroscopy. The FTS performances of the catalysts were tested in a slurry phase reactor. The characterization results indicated that Mn increased the surface area of the catalyst, and improved the dispersion of （α-Fe2O3 and reduced its crystallite size as a result of the high dispersion effect of Mn and the Fe-Mn interaction. The Fe-Mn interaction also suppressed the reduction of （α-Fe2O3 to Fe3O4, stabilized the FeO phase, and （or） decreased the carburization degree of the catalysts in the H2 and syngas reduction processes. In addition, incorporated Mn decreased the initial catalyst activity, but improved the catalyst stability because Mn restrained the reoxidation of iron carbides to Fe3O4, and improved further carburization of the catalysts. Manganese suppressed the formation of CH4 and increased the selectivity to light olefins （C2-4^=）, but it had little effect on the selectivities to heavy （C5＋） hydrocarbons. All these results indicated that the strong Fe-Mn interaction suppressed the chemisorptive effect of the Mn as an electronic promoter, to some extent, in the precipitated iron-manganese catalyst system.

Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

A systematic study was undertaken to investigate the effects of the manganese incorporation manner on the textural properties, bulk and surface phase compositions, reduction/carburization behaviors, and surface basicity of an iron-based Fischer-Tropsch synthesis （FTS） catalyst. The catalyst samples were characterized by N2 physisorption, X-ray photoelectron spectroscopy （XPS）, H2 （or CO） temperature-programmed reduction （TPR）, CO2 temperature-programmed desorption （TPD）, and M5ssbauer spectroscopy. The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor （CSTR）. The characterization results indicated that the manganese promoter incorporated by using the coprecipitation method could improve the dispersion of iron oxide, and decrease the size of the iron oxide crystallite. The manganese incorporated with the impregnation method is enriched on the catalyst＇s surface. The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H2, CO, and syngas because of the excessive enrichment of manganese on the catalyst surface. The catalyst added manganese using the coprecipitation method has the highest CO conversion （51.9%） and the lowest selectivity for heavy hydrocarbons （C12＋）.

Effect of Sulfate on an Iron Manganese Catalyst for Fischer-Tropsch Synthesis

The effect of sulfate on Fischer-Tropsch synthesis performance was investigated in a slurryphase continuously stirred tank reactor （CSTR） over a Fe-Mn catalyst. The physiochemical properties of the catalyst impregnated with different levels of sulfate were characterized by N2 physisorption, X-ray photoelectron spectroscopy （XPS）, H2 （or CO） temperature-programmed reduction （TPR）, Mossbauer spectroscopy, and CO2 temperature-programmed desorption （TPD）. The characterization results indicated that the impregnated sulfate slightly decreased the BET surface area and pore volume of the catalyst, suppressed the catalyst reduction and carburization in CO and syngas, and decreased the catalyst surface basicity. At the same time, the addition of small amounts of sulfate improved the activities of FischerTropsch synthesis （FTS） and water gas shift （WGS）, shifted the product to light hydrocarbons （C1-C11） and suppressed the formation of heavy products （C12＋）. Addition of SO4^2- to the catalyst improved the FTS activity at a sulfur loading of 0.05-0.80 g per 100 g Fe, and S-05 catalyst gave the highest CO conversion （62.3%）, and beyond this sulfur level the activity of the catalyst decreased.

Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction

Nitrogen-doped graphene is a promising candidate for the replacement of noble metal-based electrocatalysts for oxygen reduction reactions （ORRs）. The addition of pores and holes into nitrogen-doped graphene enhances the ORR activity by introducing abundant exposed edges, accelerating mass transfer, and impeding aggregation of the graphene sheets. Herein, we present a straightforward but effective strategy for generating porous holey nitrogen-doped graphene （PHNG） via the pyrolysis of urea and magnesium acetate tetrahydrate. Due to the combined effects of the in situ generated gases and MgO nanoparticles, the synthesized PHNGs featured not only numerous out-of-plane pores among the crumpled graphene sheets, but also interpenetrated nanoscale （5-15 nm） holes in the assembled graphene. Moreover, the nitrogen doping configurations of PHNG were optimized by post-thermal treatments at different temperatures. It was found that the overall content of pyridinic and quaternary nitrogen positively correlates with the ORR activity; in particular, pyridinic nitrogen generates the most desirable characteristics for the ORR. This work reveals new routes for the synthesis of PHNG-based materials and elucidates the contributions of various nitrogen species to ORRs.