Methyl radical chemistry in non-oxidative methane activation over metal single sites.

Molybdenum supported on zeolites has been extensively studied as a catalyst for methane dehydroaromatization. Despite significant progress, the actual intermediates and particularly the first C-C bond formation have not yet been elucidated. Herein we report evolution of methyl radicals during non-oxidative methane activation over molybdenum single sites, which leads selectively to value-added chemicals. Operando X-ray absorption spectroscopy and online synchrotron vacuum ultraviolet photoionization mass spectroscopy in combination with electron microscopy and density functional theory calculations reveal the essential role of molybdenum single sites in the generation of methyl radicals and that the formation rate of methyl radicals is linearly correlated with the number of molybdenum single sites. Methyl radicals transform to ethane in the gas phase, which readily dehydrogenates to ethylene in the absence of zeolites. This is essentially similar to the reaction pathway over the previously reported SiO2 lattice-confined single site iron catalyst. However, the availability of a zeolite, either in a physical mixture or as a support, directs the subsequent reaction pathway towards aromatization within the zeolite confined pores, resulting in benzene as the dominant hydrocarbon product. The findings reveal that methyl radical chemistry could be a general feature for metal single site catalysis regardless of the support (either zeolites MCM-22 and ZSM-5 or SiO2) whereas the reaction over aggregated molybdenum carbide nanoparticles likely facilitates carbon deposition through surface C-C coupling. These findings allow furthering the fundamental insights into non-oxidative methane conversion to value-added chemicals.

Versatile and high temperature spectroscopic cell for operando fluorescence and transmission x-ray absorption spectroscopic studies of heterogeneous catalysts.

A modular high-temperature cell consisting of a plug-flow microreactor with a fixed catalyst bed and long heating zone has been established for operando x-ray absorption/fluorescence spectroscopic and diffraction studies. The functionality of the cell is demonstrated for two important areas: emission control using 2 wt. % Pd/Al2O3 acting as a three-way catalyst and direct conversion of methane to olefins and aromatics on a 0.5% Fe/SiO2 catalyst. The performance has been determined by online infrared spectroscopy and mass spectrometry, respectively. In addition, the cell can be combined with optical spectroscopy, such as Raman spectroscopy. The catalyst, present as powdered/sieved samples, can be measured under reaction conditions at temperatures of up to 1050 °C. Another key aspect is a long isothermal heating zone with a small temperature gradient (<3 °C/mm at 1000 °C without reaction) including an inert zone for pre-heating of the reactant gas. Due to the small size of the microreactor and the heating system including a water cooling system, heating/cooling rates of up to 100 °C/min can be achieved. Moreover, due to the compact design and the autonomous control system, the high temperature operando setup fits to the space at the majority of synchrotron beamlines. In many cases, the concentration of the element of interest in the catalysts is low requiring x-ray absorption spectroscopy measurements in the fluorescence measurement mode. Hence, the microreactor was designed to fit such needs as well. More specifically, the case of Fe-containing catalysts was particularly considered by using iron-free materials for the reactor housing.