Erratum to: 36th International Symposium on Intensive Care and Emergency Medicine

[This corrects the article DOI: 10.1186/s13054-016-1208-6.]

Towards activity descriptors for the methane dehydroaromatization catalyst Mo/HZSM-

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.ChemE/Catalysis Engineerin

Progress in Developing a Structure-Activity Relationship for the Direct Aromatization of Methane

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.Accepted Author ManuscriptChemE/Catalysis Engineerin

Quantifying the impact of dispersion, acidity and porosity of Mo/HZSM-5 on the performance in methane dehydroaromatization

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. ChemE/Catalysis EngineeringApplied Science

Structure and Reactivity of the Mo/ZSM-5 Dehydroaromatization Catalyst: An Operando Computational Study

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.ChemE/Inorganic Systems EngineeringChemE/Catalysis EngineeringChemE/Algemee

Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization

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.Accepted Author ManuscriptChemE/Catalysis Engineerin

A site-sensitive quasi-in situ strategy to characterize Mo/HZSM-5 during activation

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.Accepted Author ManuscriptChemE/Catalysis EngineeringChemE/Inorganic Systems EngineeringChemE/Algemee

Telecom-Band Quantum Interference of Frequency-Converted Photons from Remote Detuned NV Centers

Entanglement distribution over quantum networks has the promise of realizing fundamentally new technologies. Entanglement between separated quantum processing nodes has been achieved on several experimental platforms in the past decade. To move toward metropolitan-scale quantum network test beds, the creation and transmission of indistinguishable single photons over existing telecom infrastructure is key. Here, we report the interference of photons emitted by remote spectrally detuned NV-center-based network nodes, using quantum frequency conversion to the telecom L band. We find a visibility of 0.79±0.03 and an indistinguishability between converted NV photons around 0.9 over the full range of the emission duration, confirming the removal of the spectral information present. Our approach implements fully separated and independent control over the nodes, time multiplexing of control and quantum signals, and active feedback to stabilize the output frequency. Our results demonstrate a working principle that can be readily employed on other platforms and shows a clear path toward generating metropolitan-scale solid-state entanglement over deployed telecom fibers.QuTechQID/Hanson LabQN/vanderSarlabQID/Taminiau LabQID/Software GroupBUS/TNO STAFFQN/Hanson La