Revealing Active Sites and Reaction Pathways in Methane Non-Oxidative Coupling over Iron-Containing Zeolites

Non-oxidative coupling of methane is a promising route to obtain ethylene directly from natural gas. We synthesized siliceous [Fe]zeolites with MFI and CHA topologies and found that they display high selectivity (>90 % for MFI and >99 % for CHA) to ethylene and ethane among gas-phase products. Deactivated [Fe]zeolites can be regenerated by burning coke in air. In situ X-ray absorption spectroscopy demonstrates that the isolated Fe3+ centers in zeolite framework of fresh catalysts are reduced during the reaction to the active sites, including Fe2+ species and Fe (oxy)carbides dispersed in zeolite pores. Photoelectron photoion coincidence spectroscopy results show that methyl radicals are the reaction intermediates formed upon methane activation. Ethane is formed by methyl radical coupling, followed by its dehydrogenation to ethylene. Based on the observation of intermediates including allene, vinylacetylene, 1,3-butadiene, 2-butyne, and cyclopentadiene over [Fe]MFI, a reaction network is proposed leading to polyaromatic species. Such reaction intermediates are not observed over the small-pore [Fe]CHA, where ethylene and ethane are the only gas-phase products.RST/Fundamental Aspects of Materials and EnergyRID/TS/Instrumenten groe

Impact of small promoter amounts on coke structure in dry reforming of methane over Ni/ZrO2

Coke deposition is one of the main challenges in the commercialisation of dry reforming of methane oversupported Ni catalysts. Besides the coke quantity, the structure of the deposits is also essential for thecatalyst lifetime. Accordingly, in this study, we analysed the effect of Na, K, and Cs promoters on boththese variables over Ni/ZrO2catalysts. Besides blocking the most active coke-forming sites already at lowloading, the promoting effect of the alkali metals is also contributed to by their coke gasification activity.To evaluate the additional impact of the latter, the behaviour of alkali-doped catalysts was compared tothat for Mn-doped catalysts, exclusively featuring the site-blocking promotion mechanism. While theconversion is barely affected by the type of promoter, it has a profound effect on the amount and thecomposition of carbon deposits formed during the reaction. Promoting with K or Mn reduces the cokecontent to a similar degree but with less carbon fibres observed in the case of K. The promotion by Cs andNa results in the lowest coke content. The superior performance of Cs and Na-doped Ni/ZrO2catalysts isattributed to the enhanced coke gasificationviacarbonate species on top of the site blocking effects.ChemE/Inorganic Systems EngineeringChemE/Catalysis EngineeringChemE/Algemee