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.

Metal−organic frameworks (MOFs) are the promising nanomaterials for separation of molecules with close dimensions and structures, such as various types of isomers. The efficiency of separation can be greatly enhanced if the apertures of the nanosized windows, controlling the diffusion of a particular molecule inside the cavities, are fine-tuned by external stimuli. We report the new approach for precise measurement of window sizes in ZIF-8 MOF and employ it in efficient separation of xylenes, which is of high practical importance. For this sake, we synthesized ZIF-8 with embedded stable nitroxides in the pores and applied electron paramagnetic resonance spectroscopy for in situ kinetic measurement of the diffusion of various guest molecules through the material. Slight variation of temperature within 298−333 K allowed tuning of the windows and reaching optimum conditions for separation of p-, m-, and o-xylenes with the efficiency up to 92−95%. The developed methodology provides deeper understanding of steric and kinetic aspects of molecular diffusion in ZIF-8 and paves the way to rational optimization of other MOF-based separation applications.

The one‐step synthesis and characterization of a new and robust titanium‐based metal–organic framework, ACM‐1, is reported. In this structure, which is based on infinite Ti−O chains and 4,4′,4′′,4′′′‐(pyrene‐1,3,6,8‐tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge‐separation lifetimes. The suitable energies for band gap and conduction band minimum (CBM) offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.