Desilication of highly siliceous zeolite ZSM-5 with NaOH and NaOH/tetrabutylamine hydroxide

The results of both chemical and XPS analysis pointed out that desilication of highly siliceous ZSM-5 of Si/Al = 164 was more effective in the surface zone than in the bulk, contrary to zeolite ZSM-5 of Si/Al = 31.6. According to the IR studies in parent zeolite the concentration of protonic sites was very close to the concentration of Al indicating that all Al atoms can form Si-OH-Al. The results of our quantitative IR studies strongly support the realumination thesis, i.e. some Al atoms extracted in basic solutions are subsequently reinserted forming new acidic hydroxyls. In desilicated zeolites all Al atoms were able to form protonic sites, however part of them dehydroxylated during the activation of zeolite producing Lewis acid sites according to the stoichiometry: one protonic site was transformed into one Lewis site. Low temperature nitrogen adsorption revealed that the alkaline treatment of highly siliceous zeolite with 0.2 M NaOH/TBAOH mixture produced mesopores of smaller diameter and narrower pore size distribution than in the case of zeolite of medium Si/Al ratio. This result can be explained by low concentration of Al which similarly as TBA(+) cations plays the role of pore directing agents (PDA). Contrary to TEA(+), the presence of Al in desilication mixture, led to the formation of larger pores. Therefore, in highly siliceous zeolite TBA(+) played dominant role as PDA producing narrower pores. Highly siliceous zeolite with uniform distribution of relatively narrow pores may be useful catalyst or catalyst support. The influence of desilication temperature on porosity development was also investigated. The increase of desilication temperature from 338 to 353 K resulted in both more extensive demetalation (more Si and Al is extracted) and the distinct increase of the volume and surface of mesopores. Both lower concentration of protonic sites and higher concentration of Lewis sites confirmed partial zeolite destruction upon desilication at elevated temperature. The experiments of pivalonitrile sorption followed by IR spectroscopy showed a significant increase of accessibility of acid sites to bulky pivalonitrile molecules. (C) 2012 Elsevier Inc. All rights reserved.The research was partially carried out with the equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (Contract No. POIG.02.01.00-12-023/08).Sadowska, K.; Góra-Marek, K.; Drozdek, M.; Kustrowski, P.; Datka, J.; Martínez-Triguero, J.; Rey Garcia, F. (2013). Desilication of highly siliceous zeolite ZSM-5 with NaOH and NaOH/tetrabutylamine hydroxide. Microporous and Mesoporous Materials. 168:195-205. https://doi.org/10.1016/j.micromeso.2012.09.033S19520516

Cosmic Ray Extremely Distributed Observatory: a global network of detectors to probe contemporary physics mysteries

In the past few years, cosmic-rays beyond the GZK cut-off ($E > 5 \times 10^{19}$ eV) have been detected by leading collaborations such as Pierre Auger Observatory. Such observations raise many questions as to how such energies can be reached and what source can possibly produce them. Although at lower energies, mechanisms such as Fermi acceleration in supernovae front shocks seem to be favored, top-down scenarios have been proposed to explain the existence of ultra-high energy cosmic-rays: the decay of super-massive long-lived particles produced in the early Universe may yield to a flux of ultra-high energy photons. Such photons might be presently generating so called super-preshowers, an extended cosmic-ray shower with a spatial distribution that can be as wide as the Earth diameter. The Cosmic Ray Extremely Distributed Observatory (CREDO) mission is to find such events by means of a network of detectors spread around the globe. CREDO's strategy is to connect existing detectors and create a worldwide network of cosmic-ray observatories. Moreover, citizen-science constitutes an important pillar of our approach. By helping our algorithms to recognize detection patterns and by using smartphones as individual cosmic-ray detectors, non-scientists can participate in scientific discoveries and help unravel some of the deepest mysteries in physics.Comment: excited QCD Conference, CREDO Collaboration, 7 pages, 3 figure

Search for ultra-high energy photons through preshower effect with gamma-ray telescopes: Study of CTA-North efficiency

Indexación ScopusAs ultra-high energy photons (EeV and beyond) propagate from their sources of production to Earth, radiation-matter interactions can occur, leading to an effective screening of the incident flux. In this energy domain, photons can undergo e+/e− pair production when interacting with the surrounding geomagnetic field, which in turn can produce a cascade of electromagnetic particles called preshower. Such cascade can initiate air showers in the Earth's atmosphere that gamma-ray telescopes, such as the next-generation gamma-ray observatory Cherenkov Telescope Array, can detect through Cherenkov emission. In this paper, we study the feasibility of detecting such phenomenon using Monte-Carlo simulations of nearly horizontal air showers for the example of the La Palma site of the Cherenkov Telescope Array. We investigate the efficiency of multivariate analysis in correctly identifying preshower events initiated by 40 EeV photons and cosmic ray dominated background simulated in the energy range 10 TeV – 10 EeV. The effective areas for such kind of events are also investigated and event rate predictions related to different ultra-high energy photons production models are presented. While the expected number of preshowers from diffuse emission of UHE photons for 30 hours of observation is estimated around 3.3×10−5 based on the upper limits put by the Pierre Auger Observatory, this value is at the level of 2.7×10−4 (5.7×10−5) when considering the upper limits of the Pierre Auger Observatory (Telescope Array) on UHE photon point sources. However, UHE photon emission may undergo possible ”boosting” due to gamma-ray burst, increasing the expected number of preshower events up to 0.17 and yielding a minimum required flux of ~ 0.2 km−2yr−1 to obtain one preshower event, which is about a factor 10 higher than upper limits put by the Pierre Auger Observatory and Telescope Array (0.034 and 0.019 km−2yr−1, respectively). © 2020https://www-sciencedirect-com.recursosbiblioteca.unab.cl/science/article/pii/S092765052030061X?via%3Dihu

Catalytic cracking performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility

The zeolite Beta is considered as a promising additive for FCC catalyst in diesel oil production. In this article, it is shown that hierarchical zeolite Beta obtained by an optimized desilication procedure increases diesel and propylene yields during gas oil cracking reaction. The alkaline treatment of zeolite Beta (Si/Al = 22) by desilication with NaOH and NaOH&TBAOH was investigated. The catalytic performance improvement of desilicated zeolite Beta has been rationalized by deep characterization of the samples including X-ray diffraction, low-temperature adsorption of nitrogen, solid-state 29Si MAS NMR and IR studies of acidity. Finally, the catalytic performance of the zeolites Beta was evaluated in the cracking of n-decane, 1,3,5-tri-iso-propylbenzene, and vacuum gas oil. It was found that desilication with NaOH&TBAOH ensures the more uniform intracrystalline mesoporosity with the formation of narrower mesopores, while preserving full crystallinity resulting in catalysts with the most appropriated acidity and then with better catalytic performance.Also, M.C.I.L., J.M.T. and F.R. thank financial support from the Spanish Ministry of Economy and Competitiveness through the Severo Ochoa program (SEV-2012-0267) as well as operating grants Consolider Ingenio Multicat (CSD-2009-00050) and MAT-2012-3856-0O2-01.Tarach, K.; Gora-Marek, K.; Tekla, J.; Brylewska, K.; Datka, J.; Mlekodaj, K.; Makowski, W.... (2014). Catalytic cracking performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility. Journal of Catalysis. 312:46-57. https://doi.org/10.1016/j.jcat.2014.01.009S465731

Theoretical description of hydrogen bonding in oxalic acid dimer and trimer based on the combined extended-transition-state energy decomposition analysis and natural orbitals for chemical valence (ETS-NOCV)

In the present study we have analyzed hydrogen bonding in dimer and trimer of oxalic acid, based on a recently proposed charge and energy decomposition scheme (ETS-NOCV). In the case of a dimer, two conformations, α and β, were considered. The deformation density contributions originating from NOCV’s revealed that the formation of hydrogen bonding is associated with the electronic charge deformation in both the σ—(Δρσ) and π-networks (Δρπ). It was demonstrated that σ-donation is realized by electron transfer from the lone pair of oxygen on one monomer into the empty \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rho_{H - O}^*$$\end{document} orbital of the second oxalic acid fragment. In addition, a covalent contribution is observed by the density transfer from hydrogen of H-O group in one oxalic acid monomer to the oxygen atom of the second fragment. The resonance assisted component (Δρπ), is based on the transfer of electron density from the π—orbital localized on the oxygen of OH on one oxalic acid monomer to the oxygen atom of the other fragment. ETS-NOCV allowed to conclude that the σ(O---HO) component is roughly eight times as important as π (RAHB) contribution in terms of energetic estimation. The electrostatic factor (ΔEelstat) is equally as important as orbital interaction term (ΔEorb). Finally, comparing β-dimer of oxalic acid with trimer we found practically no difference concerning each of the O---HO bonds, neither qualitative nor quantitative