Synthesis and Morphology Control of AM‐6 Nanofibers with Tailored ‐V‐O‐V‐ Intermediates

Microporous vanadosilicates with octahedral VO₆ and tetrahedral SiO₄ units, better known as AM‐6, have been hydrothermally synthesized with different morphologies by controlling the Na/K molar ratio of the initial gel mixtures. The morphology of the AM‐6 materials changed from bulky cube to nanofiber aggregates as the Na/K molar ratio decreased from 1.9 to 0.2. Raman spectroscopy revealed that the VO₃^? intermediate species plays an important role in the formation of the nanofiber morphology. The orientation of ‐V‐O‐V‐ chains in nanofiber aggregates was examined by confocal polarized micro‐Raman spectroscopy. It was found that these aggregates are assemblies of short ‐V‐O‐V‐ chains perpendicular to the axis of nanofibers. The obtained AM‐6 nanofibers greatly increase the exposed proportion of V? O terminals, and thus improve the catalytic performance.     

Platinum‐Promoted Ga/Al2O3 as Highly Active,Selective, and Stable Catalyst for the Dehydrogenation of Propane

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.     

Disentangling Reaction Processes of Zeolites within Single‐Oriented Channels

Establishing structure–reactivity relationships for specific channel orientations of zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, a well‐defined model system was developed to build structure–reactivity relationships for specific zeolite‐channel orientations during various catalytic reaction processes, for example, the methanol‐ and ethanol‐to‐hydrocarbons (MTH and ETH) process as well as oligomerization reactions. The entrapped and effluent hydrocarbons from single‐oriented zeolite ZSM‐5 channels during the MTH process were monitored by using operando UV/Vis diffuse reflectance spectroscopy (DRS) and on‐line mass spectrometry (MS), respectively. The results reveal that the straight channels favor the formation of internal coke, promoting the aromatic cycle. Furthermore, the sinusoidal channels produce aromatics, (e.g., toluene) that further grow into larger polyaromatics (e.g., graphitic coke) leading to deactivation of the zeolites. This underscores the importance of careful engineering of materials to suppress coke formation and tune product distribution by rational control of the location of zeolite acid sites and crystallographic orientations.     

Beyond Mechanical Recycling: Giving New Life to Plastic Waste

Increasing the stream of recycled plastic necessitates an approach beyond the traditional recycling via melting and re‐extrusion. Various chemical recycling processes have great potential to enhance recycling rates. In this Review, a summary of the various chemical recycling routes and assessment via life‐cycle analysis is complemented by an extensive list of processes developed by companies active in chemical recycling. We show that each of the currently available processes is applicable for specific plastic waste streams. Thus, only a combination of different technologies can address the plastic waste problem. Research should focus on more realistic, more contaminated and mixed waste streams, while collection and sorting infrastructure will need to be improved, that is, by stricter regulation. This Review aims to inspire both science and innovation for the production of higher value and quality products from plastic recycling suitable for reuse or valorization to create the necessary economic and environmental push for a circular economy.     

LambdaO4 upside down: a new molecular structure for supported VO4 catalysts

Vanadium oxide (1 wt %) supported on gamma-Al(2)O(3) was used to investigate the interface between the catalytically active species and the support oxide. Raman, UV-vis-NIR DRS, ESR, XANES, and EXAFS were used to characterize the sample in great detail. All techniques showed that an isolated VO(4) species was present at the catalyst surface, which implies that no V-O-V moiety is present. Surprisingly, a Raman band was present at 900 cm(-1), which is commonly assigned to a V-O-V vibration. This observation contradicts the current literature assignment. To further elucidate on potential other Raman assignments, the exact molecular structure of the VO(4) entity (1 V=O bond of 1.58 A and 3 V-O bonds of 1.72 A) together with its position relative to the support O anions and Al cation of the Al(2)O(3) support has been investigated with EXAFS. In combination with a structural model of the alumina surface, the arrangement of the support atoms in the proximity of the VO(4) entity could be clarified, leading to a new molecular structure of the interface between VO(4) and Al(2)O(3). It was found that VO(4) is anchored to the support oxide surface, with only one V-O support bond instead of three, which is commonly accepted in the literature. The structural model suggested in this paper leaves three possible assignments for the 900 cm(-1) band: a V-O-Al vibration, a V-O-H vibration, and a V-(O-O) vibration. The pros and cons of these different options will be discussed.     

Anomalous magnetic properties of the complex (ET)2C60

Investigations of the temperature dependences of the magnetic permeability and dielectric permittivity in the temperature range 4.2 K⩽T ⩽300 K and the field dependence of the magnetization M(B) in fields B⩽50 T show that the magnetic properties of the complex (ET)₂C₆₀ cannot be described on the basis of the standard model, which assumes that the paramagnetic oxygen impurity makes the dominant contribution. It is found that the magnetism in (ET)₂C₆₀ is due to the diamagnetic properties of the C₆₀ and ET molecules and to specific paramagnetic centers of the type C ₆₀ ⁻ , which possess an anomalously low g factor |g|≈0.14. An experimentum crucis is proposed for checking the oxygen paramagnetic center model for pure C₆₀ films. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 10, 733–738 (25 May 1999)     

Identification of Intermediates in Zeolite‐Catalyzed Reactions by In Situ UV/Vis Microspectroscopy and a Complementary Set of Molecular Simulations

The optical absorption properties of (poly)aromatic hydrocarbons occluded in a nanoporous environment were investigated by theoretical and experimental methods. The carbonaceous species are an essential part of a working catalyst for the methanol‐to‐olefins (MTO) process. In situ UV/Vis microscopy measurements on methanol conversion over the acidic solid catalysts H‐SAPO‐34 and H‐SSZ‐13 revealed the growth of various broad absorption bands around 400, 480, and 580 nm. The cationic nature of the involved species was determined by interaction of ammonia with the methanol‐treated samples. To determine which organic species contribute to the various bands, a systematic series of aromatics was analyzed by means of time‐dependent density functional theory (TDDFT) calculations. Static gas‐phase simulations revealed the influence of structurally different hydrocarbons on the absorption spectra, whereas the influence of the zeolitic framework was examined by using supramolecular models within a quantum mechanics/molecular mechanics framework. To fully understand the origin of the main absorption peaks, a molecular dynamics (MD) study on the organic species trapped in the inorganic host was essential. During such simulation the flexibility is fully taken into account and the effect on the UV/Vis spectra is determined by performing TDDFT calculations on various snapshots of the MD run. This procedure allows an energy absorption scale to be provided and the various absorption bands determined from in situ UV/Vis spectra to be assigned to structurally different species.