Istituto Nazionale di Ricerca Metrologica
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Transitioning from Methanol to Olefins (MTO) toward a Tandem CO2 Hydrogenation Process: On the Role and Fate of Heteroatoms (Mg, Si) in MAPO-18 Zeotypes
Get PDFThe tandem CO2 hydrogenation to hydrocarbons over mixed metal oxide/zeolite catalysts (OXZEO) is an efficient way of producing value-added hydrocarbons (platform chemicals and fuels) directly from CO2 via methanol intermediate in a single reactor. In this contribution, two MAPO-18 zeotypes (M = Mg, Si) were tested and their performance was compared under methanol-to-olefins (MTO) conditions (350 degrees C, PCH3OH = 0.04 bar, 6.5 gCH3OH h-1 g-1), methanol/CO/H2 cofeed conditions (350 degrees C, PCH3OH/PCO/PH2 = 1:7.3:21.7 bar, 2.5 gCH3OH h-1 g-1), and tandem CO2 hydrogenation-to-olefin conditions (350 degrees C, PCO2/PH2 = 7.5:22.5 bar, 1.4-12.0 gMAPO-18 h molCO2-1). In the latter case, the zeotypes were mixed with a fixed amount of ZnO:ZrO2 catalyst, well-known for the conversion of CO2/H2 to methanol. Focus was set on the methanol conversion activity, product selectivity, and performance stability with time-on-stream. In situ and ex situ Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), solid-state nuclear magnetic resonance (NMR), sorption experiments, and ab initio molecular dynamics (AIMD) calculations were performed to correlate material performance with material characteristics. The catalytic tests demonstrated the better performance of MgAPO-18 versus SAPO-18 at MTO conditions, the much superior performance of MgAPO-18 under methanol/CO/H2 cofeeds, and yet the increasingly similar performance of the two materials under tandem conditions upon increasing the zeotype-to-oxide ratio in the tandem catalyst bed. In situ FT-IR measurements coupled with AIMD calculations revealed differences in the MTO initiation mechanism between the two materials. SAPO-18 promoted initial CO2 formation, indicative of a formaldehyde-based decarboxylation mechanism, while CO and ketene were the main constituents of the initiation pool in MgAPO-18, suggesting a decarbonylation mechanism. Under tandem CO2 hydrogenation conditions, the presence of high water concentrations and low methanol partial pressure in the reaction medium led to lower, and increasingly similar, methanol turnover frequencies for the zeotypes. Despite both MAPO-18 zeotypes showing signs of activity loss upon storage due to the interaction of the sites with ambient humidity, they presented a remarkable stability after reaching steady state under tandem reaction conditions and after steaming and regeneration cycles at high temperatures. Water adsorption experiments at room temperature confirmed this observation. The faster activity loss observed in the Mg version is assigned to its harder Mg2+-ion character and the higher concentration of CHA defects in the AEI structure, identified by solid-state NMR and XRD. The low stability of a MgAPO-34 zeotype (CHA structure) upon storage corroborated the relationship between CHA defects and instability
Development of an anthropomorphic brain phantom for magnetic resonance-based electric properties tomography
Get PDFMeasurement and Calibration Approaches for Two-Port Scattering Parameters at mK Temperatures
No full textOptical wood with switchable solar transmittance for all-round thermal management
No full textTechnologies enabling passive daytime radiative cooling and daylight harvesting are highly relevant for energy-efficient buildings. Despite recent progress demonstrated with passively cooling polymer coatings, however, it remains challenging to combine also a passive heat gain mechanism into a single substrate for all-round thermal management. Herein, we developed an optical wood (OW) with switchable transmittance of solar irradiation enabled by the hierarchically porous structure, ultralow absorption in solar spectrum and high infrared absorption of cellulose nanofibers. After delignification, the OW shows a high solar reflectance (94.9%) in the visible and high broadband emissivity (0.93) in the infrared region (2.5–25 μm). Owing to the exceptional mass transport of its aligned cellulose nanofibers, OW can quickly switch to a new highly transparent state following phenylethanol impregnation. The solar transmittance of optical wood (OW-II state) can reach 68.4% from 250 to 2500 nm. The switchable OW exhibits efficient radiative cooling to 4.5 °C below ambient temperature in summer (cooling power 81.4 W m−2), and daylight heating to 5.6 °C above the temperature of natural wood in winter (heating power 229.5 W m−2), suggesting its promising role as a low-cost and sustainable solution to all-season thermal management applications
Comparative Study of Quasi-Solid-State Dye-Sensitized Solar Cells Using Z907, N719, Photoactive Phenothiazine Dyes and PVDF-HFP Gel Polymer Electrolytes with Different Molecular Weights
Get PDFThe present study investigates the influence of photosensitizer selection and the polymer electrolyte composition on the performance of quasi-solid-state dye-sensitized solar cells (QsDSSCs). Two benchmark ruthenium dyes, N719 and Z907, alongside a novel photoactive phenothiazine dye were used. Each dye was incorporated into a QsDSSC architecture employing poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) as the gel electrolyte matrix, with varying molecular weights, to investigate their impacts on the overall device performance and long-term stability. Our
results demonstrated that the N719 dye exhibited the highest power conversion efficiency (PCE), attributed to its strong absorption in the visible spectrum and efficient electron injection into the TiO2 photoanode. Z907, on the other hand, showed moderate PCE due to its broader absorption profile but slower electron injection kinetics. The phenothiazine dye revealed promising PCE, with tunable absorption properties and efficient charge transfer. Furthermore, the impact of PVDF-HFP polymer gel electrolytes with varying molecular weights on cell stability was explored. The QsDSSC incorporating the PVH80 polymer with the phenothiazine dye exhibited reduced dye desorption, due to the effective dye molecules’ immobilization by the gel matrix, and consequently enhanced long-term stability over 600 h. This comparative study sheds light on the interplay between dye selection, the polymer gel’s properties, and QsDSSCs’ performance. These insights are crucial in designing robust and efficient QsDSSCs for practical applications
Phosphate Glass Fibers for Biomedical Applications
No full textPhosphate glass optical fibers hold promise in biomedical applications, providing versatility for diagnosis, monitoring and treatment. Tailoring specific glass compositions enables biocompatibility and resorbability, facilitating implantation and unlocking potential for various promising applications
Time-resolved light transport in structurally anisotropic media
Get PDFStructurally anisotropic materials are ubiquitous in several application fields, yet their accurate optical characterization remains challenging due our incomplete understanding of how anisotropic light transport properties arise from the microscopic scattering coefficients. In fact, even when the dynamics of light transport is directly measured, coarse simplifications are often introduced due to a lack of established theoretical models or numerical methods. Here, we apply a general Monte Carlo implementation capable of handling direction-dependent scattering to the analysis of light transport in a sample of polytetrafluoroethylene (PTFE) tape. Using only a set of transient transmittance intensity profiles, the analysis retrieves the tensor components of the diffusive rates and the scattering coefficients along all three directions, in excellent agreement with Monte Carlo simulations
Influence of size, volume concentration and aggregation state on magnetic nanoparticle hyperthermia properties versus excitation conditions
Get PDFTreatment planning in magnetic hyperthermia requires a thorough knowledge of specific loss power of magnetic nanoparticles as a function of size and excitation conditions. Moreover, in biological tissues the magnetic nanoparticles can aggregate into clusters, making the evaluation of their heating performance more challenging because of the magnetostatic dipole–dipole interactions. In this paper, we present a comprehensive modelling analysis of 10–40 nm sized spherical magnetite (Fe3O4) nanoparticles, investigating how their heating properties are influenced by magnetic field parameters (peak amplitude and frequency), and by volume concentration and aggregation state. The analysis is performed by means of an in-house micromagnetic numerical model, which solves the Landau–Lifshitz–Gilbert equation under the assumption of single-domain nanoparticles, including thermal effects via a Langevin approach. The obtained results provide insight into how to tune hyperthermia properties by varying magnetic nanoparticle size, under different excitation magnetic fields fulfilling the Hergt–Dutz limit (frequency between 50 kHz and 1 MHz, and peak amplitude between 1 kA m−1 and 50 kA m−1). Special attention is finally paid to the role of volume concentration and aggregation order, putting in evidence the need for models able to account for stochasticity and clustering in spatial distribution, to accurately simulate the contribution of magnetostatic dipole–dipole interactions in real applications
Performance evaluation of ruthenium complexes and organic sensitizers in ZnO-based dye-sensitized solar cells
No full textRuthenium (Ru) dyes are a well-known player in the field of dye-sensitized solar cells (DSSCs) due to their high efficiency and excellent stability. Their properties and complexes have been studied for almost three decades. Although these sensitizers show better performances, their high cost makes these third-generation solar devices less economical. Organic dyes have recently been explored as an alternative to Ru-based dyes due to their easy and low-cost synthesis. A comparative performance evaluation of Ru complexes and dicyanoisophorone and rhodanine organic dyes in ZnO-based DSSCs is here reported. All the Ru complexes showed better performance in comparison to organic dyes except R-4. Among the Ru sensitizers, R-3 exhibited the highest efficiency of 1.21% followed by R-2, which is attributed to the presence of several anchoring groups such as carboxyl, nitro and amine. However, the presence of more nitrogen-based groups has drastically reduced the performance as observed for R-4, which is the least performing dye among the Ru-based ones. On the contrary, organic sensitizers S-06 and P-4 revealed to be less efficient with respect to R-3 owing to the presence of only one anchoring group and weak photoanode/dye interaction
Adaptable test bench for ASTM-compliant permeability measurement of porous scaffolds for tissue engineering
Get PDFIntrinsic permeability describes the ability of a porous medium to be penetrated by a fluid. Considering porous scaffolds for tissue engineering (TE) applications, this macroscopic variable can strongly influence the transport of oxygen and nutrients, the cell seeding process, and the transmission of fluid forces to the cells, playing a crucial role in determining scaffold efficacy. Thus, accurately measuring the permeability of porous scaffolds could represent an essential step in their optimization process. In literature, several methods have been proposed to characterize scaffold permeability. Most of the currently adopted approaches to assess permeability limit their applicability to specific scaffold structures, hampering protocols standardization, and ultimately leading to incomparable results among different laboratories. The content of novelty of this study is in the proposal of an adaptable test bench and in defining a specific testing protocol, compliant with the ASTM International F2952-22 guidelines, for reliable and repeatable measurements of the intrinsic permeability of TE porous scaffolds. The developed permeability test bench (PTB) exploits the pump-based method, and it is composed of a modular permeability chamber integrated within a closed-loop hydraulic circuit, which includes a peristaltic pump and pressure sensors, recirculating demineralized water. A specific testing protocol was defined for characterizing the pressure drop associated with the scaffold under test, while minimizing the effects of uncertainty sources. To assess the operational capabilities and performance of the proposed test bench, permeability measurements were conducted on PLA scaffolds with regular (PS) and random (RS) micro-architecture and on commercial bovine bone matrix-derived scaffolds (CS) for bone TE. To validate the proposed approach, the scaffolds were as well characterized using an alternative test bench (ATB) based on acoustic measurements, implementing a blind randomized testing procedure. The consistency of the permeability values measured using both the test benches demonstrated the reliability of the proposed approach. A further validation of the PTB's measurement reliability was provided by the agreement between the measured permeability values of the PS scaffolds and the theory-based predicted permeability value. Once validated the proposed PTB, the performed measurements allowed the investigation of the scaffolds' transport properties. Samples with the same structure (guaranteed by the fused-deposition modeling technique) were characterized by similar permeability values, and CS and RS scaffolds showed permeability values in agreement with the values reported in the literature for bovine trabecular bone. In conclusion, the developed PTB and the proposed testing protocol allow the characterization of the intrinsic permeability of porous scaffolds of different types and dimensions under controlled flow regimes, representing a powerful tool in view of providing a reliable and repeatable framework for characterizing and optimizing scaffolds for TE applications