Abstract
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•A suite of catalysts are synthesized using IWI, SIE and CVD with different Mo precursors and their performance is compared.•Mo dispersion, Brønsted acid site density and porosity are quantified and the effect on catalytic performance determined.•Catalytic performance is most dependent on the number of Mo cationic sites present on the catalyst.•Mo nanoparticles on the outer surface of the zeolite delay the onset of aromatics formation and lead to faster deactivation.
The catalytic performance of the bifunctional catalyst Mo/HZSM-5 for methane dehydroaromatization (MDA) depends on the Mo dispersion and on zeolite acidity. Here we separately quantify the effect of dispersion and the effect of acidity on aromatic yields and coke selectivity. Also, the effect of porosity on the same is quantitatively assessed. For that, a suite of 17 samples with varying Mo dispersion were synthesized by means of several methods, including chemical vapor deposition with MoCl5, MoO2Cl2 and Mo(CO)6 as precursors and the conventional methods, incipient wetness impregnation and solid ion exchange. These catalysts were characterized with pyridine IR-spectroscopy, XPS, UV–vis spectroscopy, N2 adsorption, XRD, TGA and 27Al MAS NMR. The combined results yielded a measure of how much Mo is anchored to the zeolite as well-defined cationic species and how much is present as bigger clusters on the outer surface of the zeolite. Through relating these characterization results to the catalytic behavior of the catalysts, it was found that the maximum instantaneous benzene and naphthalene yields as well as the integral selectivities during methane dehydroaromatization linearly increase with the amount of Mo present as mono- or dimeric species. At the same time, the selectivity to coke increases with the amount of Mo present as bigger clusters or nanoparticles on the outer surface of the zeolite. The number of Mo cationic sites is the most important factor determining the activity of Mo/HZSM-5 for low loadings of Mo. But at higher loadings, the high rate of aromatics formation requires an easily accessible pore structure as well.