DFT insights into competing mechanisms of guaiacol hydrodeoxygenation on a platinum cluster

In a scenario of declining fossil resources and increasing demand for renewable and sustainable alternatives, biomass is the only source able to offer an easy and gradual transition in the use of current energy technologies based on the exploitation of carbon derivatives. Its conversion to liquid fuels has oriented our study towards the computational mechanistic analysis of the guaiacol catalytic hydrodeoxygenation, which is currently considered one of the most challenging routes for upgrading biomass-derived bio-oils. For this purpose, a subnanometric Pt10 platinum cluster was chosen as the catalyst model, with Pt as a computational reference element for catalytic hydrogenation, and guaiacol as a model compound of bio-oils. DFT calculations revealed that the energy barriers related to the cleavage of C(sp2)-O bonds in the direct deoxygenation mechanism are significantly lower (by an average of 60 kJ mol−1) than those in the deoxygenation-through-hydrogenation mechanism in which C(sp3)-O bond breaking from a saturated ring occurs. Even if the ring hydrogenation is easier in the oxygenated compound, the analysis reveals that the direct deoxygenation mechanism is favoured at all temperatures. Furthermore, the results obtained highlight that, from a thermodynamic perspective, the removal of oxygen groups preferentially occurs by the elimination of the -OCH3 fragment as methanol and then of the -OH fragment as a water molecule

DFT Study of Pt Particle Growth inside β-Zeolite Cages

The preferred location and the corresponding energetics of zeolite-embedded single metal atoms and small metal particles are hot topics within active site optimization and catalyst tuning, even as part of bifunctional materials design. In this context, periodic density functional theory was used to provide insights on the interactions of a platinum atom with the microporous cages of a purely silicious β-zeolite (BEA) framework. Cluster growth was subsequently addressed, up to Pt3@BEA systems, following a one-by-one platinum atom addition; platinum migration between cages was taken into account as well. An unbiased approach was employed, which allowed a wide panorama of structures being considered in addition to a thorough analysis in terms of energetics, cluster geometries, and cavity distortions. Calculations revealed that the optimal interaction geometry for a single platinum atom is realized where two strong Pt-O bonds in almost linear arrangement can form, regardless of the cavity involved. This can cause distortions or even breaking of the zeolite structure, a factor which however is not decisive in determining the energetics of systems with two and three platinum atoms. Platinum migration is associated with energy barriers ranging from 100 to 200 kJ mol-1, depending on the cages. Up to the dimensions considered here, preference for clustering is observed, being the embedded Pt3 systems in almost all cases energetically favored with respect to isolated atoms within the BEA framework

DFT study on zeolites’ intrinsic Brønsted acidity: The case of BEA

Since Brønsted acidity is a crucial aspect for the applications of zeolitic materials in heterogeneous catalysis, great effort was devolved to characterize the number, strength and location of the potentially active acidic sites. Quantum chemical calculations can turn out essential in estimating the intrinsic acidity by computing deprotonation energy (DPE) values, although each method comes with its own difficulties. In this context, three approaches within density functional theory were employed to study the intrinsic acidity of 30 topologically distinct Brønsted sites in the β-zeolite framework. Advantages and disadvantages of the three methods were outlined and the acidity order between the sites was assessed, being the DPE range 59 kJ mol−1 wide, with the proposed best approach. By dividing the range into three portions, the sites were classified as having high, medium and low acidity. Hydrogen bonds formation was found to be a contributing factor in determining a low Brønsted acidity

Saturated phase densities of (CO2 + H2O) at temperatures from (293 to 450) K and pressures up to 64 MPa

An apparatus consisting of an equilibrium cell connected to two vibrating tube densimeters and two syringe pumps was used to measure the saturated phase densities of (CO2 + H2O) at temperatures from (293 to 450) K and pressures up to 64 MPa, with estimated average standard uncertainties of 1.5 kg · m−3 for the CO2-rich phase and 1.0 kg · m−3 for the aqueous phase. The densimeters were housed in the same thermostat as the equilibrium cell and were calibrated in situ using pure water, CO2 and helium. Following mixing, samples of each saturated phase were displaced sequentially at constant pressure from the equilibrium cell into the vibrating tube densimeters connected to the top (CO2-rich phase) and bottom (aqueous phase) of the cell. The aqueous phase densities are predicted to within 3 kg · m−3 using empirical models for the phase compositions and partial molar volumes of each component. However, a recently developed multi-parameter equation of state (EOS) for this binary mixture, Gernert and Span [32], was found to under predict the measured aqueous phase density by up to 13 kg · m−3. The density of the CO2-rich phase was always within about 8 kg · m−3 of the density for pure CO2 at the same pressure and temperature; the differences were most positive near the critical density, and became negative at temperatures above about 373 K and pressures below about 10 MPa. For this phase, the multi-parameter EOS of Gernert and Span describes the measured densities to within 5 kg · m−3, whereas the computationally-efficient cubic EOS model of Spycher and Pruess (2010), commonly used in simulations of subsurface CO2 sequestration, deviates from the experimental data by a maximum of about 8 kg · m−3

CPO and quantitative textural analyses within sheath folds

Acknowledgments This has been a multi-national collaboration from authors based in Europe, North America, Australia and India. Erasmus funding to GIA in 2018 enabled a visit to Catania leading to discussion and initiation of this project. The authors are grateful to Amarnath Dandapat for preparation of superpolished rock thin sections at the Department of Geology and Geophysics (IIT Kharagpur, India). Niloy Bhowmik is thanked for assistance with SEM-EBSD data generation in the Central Research Facility (IIT Kharagpur, India). E.F. thanks Sibio Carmelo for thin sections preparation at the University of Turin (Italy). Authors are grateful to ANSTO laboratory personnel for the preparation of specimens (funded proposals: P9835 with the title “Sheath fold texture characterisation”, principal scientist: E.F.; co-proposers: G.I.A. and V.L.; DB6749 with the title “Texture analysis of rocks”, principal scientist: V.L.; co-proposer: E.F.; DB9606 with the title “A pilot experiment for texture characterisation in a sheath fold”, principal scientist: E.F..; co-proposers: G.I.A. and V.L.). L.N. and R.G. report that this publication has been assigned the NRCan contribution number 20230109. Many thanks to Richard D. Law and an anonymous reviewer for their careful revision that substantially improved the original version of the manuscript. We also thanks Dr. T.K. Cawood from the Geological Survey of Canada for her useful comments on the drafted manuscript. The editorial handling by Fabrizio Agosta is greatly appreciated.Peer reviewedPublisher PD

New Eco-gas mixtures for the Extreme Energy Events MRPCs: results and plans

The Extreme Energy Events observatory is an extended muon telescope array, covering more than 10 degrees both in latitude and longitude. Its 59 muon telescopes are equipped with tracking detectors based on Multigap Resistive Plate Chamber technology with time resolution of the order of a few hundred picoseconds. The recent restrictions on greenhouse gases demand studies for new gas mixtures in compliance with the relative requirements. Tetrafluoropropene is one of the candidates for tetrafluoroethane substitution, since it is characterized by a Global Warming Power around 300 times lower than the gas mixtures used up to now. Several mixtures have been tested, measuring efficiency curves, charge distributions, streamer fractions and time resolutions. Results are presented for the whole set of mixtures and operating conditions, %. A set of tests on a real EEE telescope, with cosmic muons, are being performed at the CERN-01 EEE telescope. The tests are focusing on identifying a mixture with good performance at the low rates typical of an EEE telescope.Comment: 8 pages, 6 figures, proceedings for the "XIV Workshop on Resistive Plate Chambers and Related Detectors" (19-23 February 2018), Puerto Vallarta, Jalisco State, Mexic

A simulation tool for MRPC telescopes of the EEE project

The Extreme Energy Events (EEE) Project is mainly devoted to the study of the secondary cosmic ray radiation by using muon tracker telescopes made of three Multigap Resistive Plate Chambers (MRPC) each. The experiment consists of a telescope network mainly distributed across Italy, hosted in different building structures pertaining to high schools, universities and research centers. Therefore, the possibility to take into account the effects of these structures on collected data is important for the large physics programme of the project. A simulation tool, based on GEANT4 and using GEMC framework, has been implemented to take into account the muon interaction with EEE telescopes and to estimate the effects on data of the structures surrounding the experimental apparata.A dedicated event generator producing realistic muon distributions, detailed geometry and microscopic behavior of MRPCs have been included to produce experimental-like data. The comparison between simulated and experimental data, and the estimation of detector resolutions is here presented and discussed

Structural setting of a transpressive shear zone: Insights from geological mapping, quartz petrofabric and kinematic vorticity analysis in NE Sardinia (Italy)

The Posada-Asinara Line is a crustal-scale transpressive shear zone affecting the Variscan basement in northern Sardinia during Late Carboniferous time. We investigated a structural transect of the Posada-Asinara Line (Baronie) with the aid of geological mapping and structural analysis. N-verging F2 isoclinal folds with associated mylonitic foliation (S2) are the main deformation features developed during the Posada-Asinara Line activity (D2). The mineral assemblages and microstructures suggest that the Posada-Asinara Line was affected by a retrograde metamorphic path. This is also confirmed by quartz microstructures, where subgrain rotation recrystallization superimposes on grain boundary migration recrystallization. Crystallographic preferred orientation data, obtained using electron backscatter diffraction, allowed analysis of quartz slip systems and estimation of the deformation temperature, vorticity of flow and rheological parameters (flow stress and strain rate) during the Posada-Asinara Line activity. Quartz deformation temperatures of 400 ± 50 °C have been estimated along a transect perpendicular to the Posada-Asinara Line, in agreement with the syn-kinematic post-metamorphic peak mineral assemblages and the late microstructures of quartz. The D2 phase can be subdivided in two events: an early D2early phase, related to the metamorphic peak and low kinematic vorticity (pure shear dominated), and a late D2late phase characterized by a lower metamorphic grade and an increased kinematic vorticity (simple shear dominated). Palaeopiezometry and strain rate estimates associated with the D2late deformation event showed an intensity gradient increasing towards the core of the shear zone. The D2early deformation developed under peak temperature conditions, while the D2late event was active at shallower structural levels