Mo/ZSM-5 is one of the most studied and efficient catalysts for the dehydroaromatization of methane (MDA), but the mechanism of its operation remains controversial. Here, we combine an ab initio thermodynamic analysis with a comprehensive mechanistic density functional theory study to address Mo-speciation in the zeolite and identify the active sites under the reaction conditions. We show that the exposure of Mo/ZSM-5 to the MDA conditions yields a range of reduced sites including mono- and binuclear Mo-oxo and Mo-carbide complexes. These sites can catalyze the MDA reaction via two alternative reaction channels, namely, the C-C coupling (ethylene) and the hydrocarbon-pool propagation mechanisms. Our calculations point toward the binuclear Mo-carbide species operating through the hydrocarbon-pool mechanism to be the most catalytically potent species. Although all other Mo sites in the activated catalyst can promote C-H activation in methane, they fail to provide a successful path to the desirable low-molecular-weight products.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.@en

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 MoCl 5 , MoO 2 Cl 2 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, N 2 adsorption, XRD, TGA and 27 Al 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. @en

The active sites on the methane dehydroaromatization (MDA) catalyst Mo/HZSM-5 are very hard to characterize, because they are present in various geometries and sizes and only form under reaction conditions with methane at 700 °C. To address these issues an experimental strategy is presented that enables distinguishing different active sites for MDA present on Mo/HZSM-5 and helps determining the Mo charge, nuclearity and chemical composition. This approach combines a CO pretreatment to separate the active Mo site formation from coke formation, quasi-in situ spectroscopic observations using DNP, 13C NMR, CO IR and theory. This allows the discrimination between three different types of active sites. Distinct spectroscopic features were observed corresponding to two types of mono- or dimeric Mo (oxy-)carbide sites as well as a third site assigned to Mo2C nanoparticles on the outer surface of the zeolite. Their formal Mo oxidation state was found to be between 4+ and 6+. Dynamic nuclear polarization (DNP) measurements of samples carburized in CO as well as in CH4 confirm the assignment and also show that accumulated aromatic carbon covers the bigger Mo nanoparticles on the outer surface of the zeolite, causing deactivation. It was previously observed that after an initial period where no desired products are formed yet, benzene starts slowly forming until reaching its maximum productivity. Direct observation of the active site with 13C NMR confirmed that Mo-sites do not transform further once benzene starts forming, meaning that they are fully activated during the period where no desired products are observed yet. Therefore the slow increase of the benzene formation rate cannot be attributed to a further transformation of Mo sites.@en

In view of rising global demand for aromatics as starting chemical for many commodity goods as well as pharmaceuticals, new routes for production are explored. Since the advent of fracking, natural gas has become increasingly cheap and direct utilization for aromatics production has gained attractiveness. Methane dehydroaromatization represents the most direct of such utilization routes and could potentially be very carbon efficient, if no oxidants are added, since byproducts such as CO and CO2 are avoided. For the direct non-oxidative conversion however, fast deactivation due to coke formation and significant thermodynamic limitations still stand in the way of commercialization. Improvements of the catalysts towards coke-resistance and overall stability could significantly speed up the development towards large-scale operation of the methane dehydroaromatization process, although innovation in process development is also believed to be important. It is desirable to develop a catalyst that outperforms the state-of-the-art system Mo/HZSM-5. This system however, continues to perform better than other catalyst formulations, and for 25 years already, no significantly better system was found. Thus, this thesis focusses on developing a fundamental understanding of why this catalytic system continues to outperform other systems. The aim of this thesis was to spot the characteristic traits of this catalyst, which can then be used as guidelines for the development of novel catalysts.@en

To secure future supply of aromatics, methane is a commercially interesting alternative feedstock. Direct conversion of methane into aromatics combines the challenge of activating one of the strongest C-H bonds in all hydrocarbons with the selective aromatization over zeolites. To address these challenges, smart catalyst and process design are a must. And for that, understanding the most important factors leading to successful methane C-H bond activation and selective aromatization is needed. In this review, we summarize mechanistic insight that has been gained so far not only for this reaction, but also for other similar processes involving aromatization reactions over zeolites. With that, we highlight what can be learnt from similar processes. In addition, we provide an overview of characterization tools and strategies, which are useful to gain structural information about this particular metal-zeolite system at reaction conditions. Here we also aim to inspire future characterization work, by giving an outlook on characterization strategies that have not yet been applied for the methane dehydroaromatization catalyst, but are promising for this system.@en

The mechanism of methane activation on Mo/HZSM-5 is poorly described, despite the great interest in methane dehyd roa romatization (MDA) to replace oil refineries for producing aromatics. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide, the active site for MDA can be isolated and studied without the formation of coke. This strategy helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (1 3 C H 4 ) . We show that carbon originating from the preformed carbide is incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic nature of these active sites.@en

The mechanism of methane activation on Mo/HZSM-5 is poorly described, despite the great interest in methane dehyd roa romatization (MDA) to replace oil refineries for producing aromatics. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide, the active site for MDA can be isolated and studied without the formation of coke. This strategy helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (1 3 C H 4 ) . We show that carbon originating from the preformed carbide is incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic nature of these active sites.@en

Methane dehydroaromatization (MDA) over Mo/HZSM-5 has been hypothesized in literature to proceed via a two-step mechanism: methane is first converted to ethylene on the molybdenum (Mo) functionality and then ethylene is oligomerized, cyclized and dehydrogenated on the Brønsted acid sites (BAS) of the HZSM-5 support. This hypothesis is tested by studying the conversion of ethylene at the same conditions as used for MDA, namely 700 °C, atmospheric pressure, and by co-feeding experiments with H2 and CH4. Our results suggest that ethylene is not the main intermediate for MDA, because the aromatic selectivities obtained from methane conversion are higher than selectivities measured during ethylene conversion. Furthermore, carbonaceous deposits formed during MDA have a lower density, are more hydrogenated and more active than the ones formed during ethylene aromatization (EDA). Similarly as for MDA, an activation period in which Mo carburizes to its active phase and an induction period, in which aromatics formation rates increase to their maximum are observed for ethylene conversion. The induction period, which was explained by the buildup of a hydrocarbon pool (HCP) is much faster with methane than with ethylene. This period, is attributed to a slow buildup of hydrocarbons, strongly adsorbed on Mo sites, because it is only observed with catalysts containing Mo. Hydrogen co-feeding with ethylene leads to the formation of more reactive coke species and a significantly prolonged lifetime of the catalyst, but not to a faster buildup of the HCP.@en

The mechanism of methane activation on Mo/HZSM-5 is not yet fully understood, despite the great interest in methane dehydroaromatization (MDA) to replace aromatics production in oil refineries. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide (CO), the MDA active site formation was isolated from coke formation. With this a clear 13C NMR signal solely from the active site and not obscured by coke was obtained, and it revealed two types of likely molecular Mo (oxy-)carbidic species in addition to the β-Mo2C nanoparticles often mentioned in the literature. Furthermore, separating the active site formation from coking by pre-carburization helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (13CH4). Carbon originating from the pre-formed carbide was incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic behavior of the (oxy-)carbidic active sites.@en

Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.@en

The combination of well-defined acid sites, shape-selective properties and outstanding stability places zeolites among the most practically relevant heterogeneous catalysts. The development of structure–performance descriptors for processes that they catalyse has been a matter of intense debate, both in industry and academia, and the direct conversion of methanol to olefins is a prototypical system in which various catalytic functions contribute to the overall performance. Propylene selectivity and resistance to coking are the two most important parameters in developing new methanol-to-olefin catalysts. Here, we present a systematic investigation on the effect of acidity on the performance of the zeolite ‘ZSM-5’ for the production of propylene. Our results demonstrate that the isolation of Brønsted acid sites is key to the selective formation of propylene. Also, the introduction of Lewis acid sites prevents the formation of coke, hence drastically increasing catalyst lifetime.@en

The combination of well-defined acid sites, shape-selective properties and outstanding stability places zeolites among the most practically relevant heterogeneous catalysts. The development of structure–performance descriptors for processes that they catalyse has been a matter of intense debate, both in industry and academia, and the direct conversion of methanol to olefins is a prototypical system in which various catalytic functions contribute to the overall performance. Propylene selectivity and resistance to coking are the two most important parameters in developing new methanol-to-olefin catalysts. Here, we present a systematic investigation on the effect of acidity on the performance of the zeolite ‘ZSM-5’ for the production of propylene. Our results demonstrate that the isolation of Brønsted acid sites is key to the selective formation of propylene. Also, the introduction of Lewis acid sites prevents the formation of coke, hence drastically increasing catalyst lifetime.@en

Producing aromatics directly from the smallest hydrocarbon building block, methane, is attractive because it could help satisfy increasing demand for aromatics while filling the gap created by decreased production from naphtha crackers. The system that catalyzes the direct methane dehydroaromatization (MDA) best so far is Mo supported on zeolite. Mo has shown to outperform other transition metals (TMs). Here we attempt to explain the superiority of Mo by directly comparing Fe and Mo supported on HZSM-5 zeolite. To determine the most important parameters responsible for the superior performance of Mo, detailed characterization using X-ray absorption spectroscopy (XAS) techniques combined with catalytic testing and theoretical calculations are performed. The higher abundance of mono- A nd dimeric sites for the Mo system, their ease of carburization in methane, as well as intrinsically lower activation energy barriers of breaking the methane C-H bond over Mo explain the better catalytic performance. In addition, a pretreatment in CO is presented to more easily carburize Fe and thereby improve its catalytic performance.@en