Non‐oxidative dehydroaromatization of methane (MDA) is a promising catalytic process for direct valorization of natural gas to liquid hydrocarbons. The application of this reaction in practical technology is hindered by a lack of understanding about the mechanism and nature of the active sites in benchmark zeolite‐based Mo/ZSM‐5 catalysts, which precludes the solution of problems such as rapid catalyst deactivation. By applying spectroscopy and microscopy, it is shown that the active centers in Mo/ZSM‐5 are partially reduced single‐atom Mo sites stabilized by the zeolite framework. By combining a pulse reaction technique with isotope labeling of methane, MDA is shown to be governed by a hydrocarbon pool mechanism in which benzene is derived from secondary reactions of confined polyaromatic carbon species with the initial products of methane activation.
Surface carbon (coke, carbonaceous deposits) is an integral aspect of methane dehydroaromatization catalyzed by Mo/zeolites. We investigated the evolution of surface carbon species from the beginning of the induction period until the complete catalyst deactivation by the pulse reaction technique, TGA, 13C NMR, TEM, and XPS. Isotope labeling was performed to confirm the catalytic role of confined carbon species during MDA. It was found that “hard” and “soft” coke distinction is mainly related to the location of coke species inside the pores and on the external surface, respectively. In addition, MoO3 species act as an active oxidation catalyst, reducing the combustion temperature of a certain fraction of coke. Furthermore, after dissolving the zeolite framework by HF, we found that coke formed during the MDA reaction inside the zeolite pores is essentially a zeolite-templated carbon material. The possibility of preparing zeolite-templated carbons from the most available hydrocarbon feedstock is important for the development of these interesting materials.
The one-pot Diels–Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p-xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.
Non-oxidative dehydroaromatization of methane (MDA) is apromising catalytic process for direct valorization of natural gas to liquid hydrocarbons.T he application of this reaction in practical technology is hindered by al acko f understanding about the mechanism and nature of the active sites in benchmark zeolite-based Mo/ZSM-5 catalysts,w hich precludes the solution of problems such as rapid catalyst deactivation. By applying spectroscopya nd microscopy, it is shown that the active centers in Mo/ZSM-5 are partially reduced single-atom Mo sites stabilized by the zeolite framework. By combining ap ulse reaction techniquew ith isotope labeling of methane,M DA is shown to be governed by ah ydrocarbon pool mechanism in whichb enzenei sd erived from secondary reactions of confined polyaromatic carbon species with the initial products of methane activation.The abundance of natural gas reserves calls for the development of an efficient conversion technology to upgrade its principal component, methane,i nto easily transportable chemicals.[1] Several catalytic technologies,w hich could replace the current indirect route involving an expensive synthesis gas generation step,a re being considered. Broadly, we can distinguish between oxidative and non-oxidative direct routes.[2] Among the non-oxidative approaches,c atalytic methane dehydroaromatization (MDA) is one of the most promising methods.A fter the initial reports on MDA almost three decades ago, [3] as ubstantial body of literature has appeared.[4] Thei ndustrial implementation of the MDA process is mainly hindered by rapid catalyst deactivation caused by the deposition of ac arbonaceous material that blocks the catalytically active sites. [5] Although there have been remarkable achievements in regeneration procedures, [6] developing astable MDAcatalyst is still required to arrive at acommercial process.Aprogress in this direction is seriously hampered by limited understanding of the active sites in the benchmark Mo/ZSM-5 catalyst and the mechanism of methane conversion to benzene and hydrogen. Despite considerable debate on the nature of the active phase,t here is ag rowing consensus that the active sites are confined as highly dispersed Mo species by the zeolite pores in working Mo/ZSM-5 catalysts and that Mo 2 Cn anoparticles on the external surface are inactive. [7] Concerning the reaction mechanism, most reports support ab ifunctional pathway in which methane is activated and coupled to ethylene over Mocarbide species,followed by ethylene aromatization over the zeolite Brønsted acid sites. [8] Important challenges in gaining insight into these aspects are the high reaction temperature at which the MDAreaction takes place and its transient nature,w hich involves rapid activation and deactivation stages when the fresh Mo/ZSM-5 catalyst is exposed to am ethane feed. These factors complicate operando spectroscopy and kinetic investigations.A valuable approach in this regard is to increase the temporal resolution by pulsing the reactant over the catalyst an...
Quantum chemistry-based codes and methods provide valuable computational tools to estimate reaction energetics and elucidate reaction mechanisms. Electronic structure methods allow directly studying the chemical transformations in molecular systems involving breaking and making of chemical bonds and the associated changes in the electronic structure. The link between the electronic structure and chemical bonding can be provided through the crystal orbital Hamilton population (COHP) analysis that allows quantifying the bond strength by computing Hamilton-weighted populations of localized atomic orbitals. Another important parameter reflecting the nature and strength of a chemical bond is the bond order that can be assessed by the density derived electrostatic and chemical (DDEC6) method which relies on an electron and spin density-partitioning scheme. Herein, we describe a linear correlation that can be established between the DDEC6-derived bond orders and the bond strengths computed with the COHP formalism. We demonstrate that within defined boundaries, the COHP-derived bond strengths can be consistently compared among each other and linked to the DDEC6-derived bond orders independent of the used model. The validity of these correlations and the effective model independence of the electronic descriptors are demonstrated for a variety of gas-phase chemical systems, featuring different types of chemical bonds. Furthermore, the applicability of the derived correlations to the description of complex reaction paths in periodic systems is demonstrated by considering the zeolite-catalyzed Diels–Alder cycloaddition reaction between 2,5-dimethylfuran and ethylene.
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