Enhancement of CO2/CH4 separation performances of 6FDA-based co-polyimides mixed matrix membranes embedded with UiO-66 nanoparticles

Metal-organic frameworks (MOFs) incorporation into mixed matrix membranes (MMMs) is gaining more attention due to the combined advantages of high separation performance and easy processability. Nanoparticles (NPs) of CO2-philic MOF UiO-66 (Zr-BDC) were synthesized with high surface area and ca. 50 nm particle size (and also for comparison with 100 and 200 nm sizes). They were incorporated into three 6FDA-based co-polyimides (namely 6FDA-BisP, 6FDA-ODA, and 6FDA-DAM), forming MMMs with loadings in the 4–23 wt% range. The NPs and MMMs were characterized accordingly by XRD, BET, SEM, TEM, FTIR, and TGA. CO2 and CH4 isotherms on the NPs were measured by a static volumetric method at the pressure up to 10 bar. Fractional free volume (FFV) was calculated using solid density, measured by pycnometer. Gas separation performance was evaluated using a feed composition of 50%:50% CO2:CH4 binary mixture at 35 °C and a pressure difference of 2 bar. The presence of UiO-66 NPs in the continuous 6FDA-BisP and 6FDA-ODA co-polyimides improved both CO2 permeability and CO2/CH4 selectivity by 50–180% and 70–220%, respectively. In the case of 6FDA-DAM MMMs, the CO2 permeability was significantly improved by 92%, while maintaining the CO2/CH4 selectivity. The best results in terms of CO2/CH4 selectivity were 41.9 for 6FDA-BisP (17 wt% filler loading, 108 Barrer of CO2), 57.0 for 6FDA-ODA (7 wt% filler loading, 43.3 Barrer of CO2) and 32.0 for 6FDA-DAM (8 wt% filler loading, 1728 Barrer of CO2)

Air conditioning production by a single effect absorption cooling machine directly coupled to a solar collector field. Application to Spanish climates

Due to the increasing energy consumption of air conditioning in buildings and the need to decrease the fossil CO2 emissions to the environment, the interest of using renewable energy sources shows up stronger than ever. We present a general study whose aim is to propose a method to evaluate an upper bound in the potential of solar cooling by using some simplified models. As an example it has been applied to the very diverse climates of Spain. In the paper it has been assumed a direct solar coupling between the solar collector field and a single effect absorption cooling machine, without any intermediate solar storage tank. An equation is obtained that shows the dependence of the generator/solar-collectors equilibrium temperature on basic design parameters of the system (absorption machine-solar collectors). The paper analyzes the effect of these on the total amount of cooling produced along a typical mean year and the peak cooling power. The paper also includes a discussion on how to estimate the values and what is their physical meaning of the parameters which define the behavior of real absorption machines. Finally tables are included for the 12 climates of Spain that can be used as an example of how to make a quick pre-sizing of such direct coupled system. The classification of the Spanish climates is based on general data (average monthly total horizontal solar radiation, average monthly dry temperature, etc.) and the results could be generalized for climates with the same severity. Moreover if hourly weather data is available for any place (like tmy2, bin, epw, etc. files), the procedure can be applied without further changes.Sarabia Escrivà, EJ.; Lamas Sivila, EV.; Soto Francés, VM. (2011). Air conditioning production by a single effect absorption cooling machine directly coupled to a solar collector field. Application to Spanish climates. Solar Energy. 85(9):2108-2121. doi:10.1016/j.solener.2011.05.019S2108212185

High-pressure CO2/CH4 separation of Zr-MOFs based mixed matrix membranes

The gas separation properties of 6FDA-DAM mixed matrix membranes (MMMs) with three types of zirconium-based metal organic framework nanoparticles (MOF NPs, ca. 40 nm) have been investigated up to 20 bar. Both NPs preparation and MMMs development were presented in an earlier publication that reported outstanding CO2/CH4 separation performances (50:50 vol% CO2/CH4 feed at 2 bar pressure difference, 35 °C) and this subsequent study is to demonstrate its usefulness to the natural gas separation application. In the current work, CO2/CH4 separation has been investigated at high pressure (2–20 bar feed pressure) with different CO2 content in the feed (10–50 vol%) in the temperature range 35–55 °C. Moreover, the plasticization, competitive sorption effects, and separation of the acid gas hydrogen sulfide (H2S) have been investigated in a ternary feed mixture of CO2:H2S:CH4 (vol% ratio of 30:5:65) at 20 bar and 35 °C. The incorporation of the Zr-MOFs in 6FDA-DAM enhances both CO2 permeability and CO2/CH4 selectivity of this polymer. These MMMs exhibit high stability under separation conditions relevant to an actual natural gas sweetening process. The presence of H2S does not induce plasticization but increases the total acid gas permeability, acid gas/CH4 selectivity and only causes reversible competitive sorption. The overall study suggests a large potential for 6FDA-DAM Zr-MOF MMMs to be applied in natural gas sweetening, with good performance and stability under the relevant process conditions

Sonocrystallisation of ZIF-8 in water with high excess of ligand: Effects of frequency, power and sonication time

A systematic study on the sonocrystallisation of ZIF-8 (zeolitic imidazolate framework-8) in a water-based system was investigated under different mixing speeds, ultrasound frequencies, calorimetric powers and sonication time. Regardless of the synthesis technique, pure crystals of ZIF-8 with high BET (Brunauer, Emmett and Teller) specific surface area (SSA) can be obtained in water after only 5 s. Furthermore, 5 s sonication produced even smaller crystals (~0.08 µm). The type of technique applied for producing the ZIF-8 crystals did not have any significant impact on crystallinity, purity and yield. Crystal morphology and size were affected by the use of ultrasound and mixing, obtaining nanoparticles with a more spherical shape than in silent condition (no ultrasound and mixing). However, no specific trends were observed with varying frequency, calorimetric power and mixing speed. Ultrasound and mixing may have an effect on the nucleation step, causing the fast production of nucleation centres. Furthermore, the BET SSA increased with increasing mixing speed. With ultrasound, the BET SSA is between the values obtained under silent condition and with mixing. A competition between micromixing and shockwaves has been proposed when sonication is used for ZIF-8 production. The former increases the BET SSA, while the latter could be responsible for porosity damage, causing a decrease of the surface area. © 2021 The Author(s

"Razne vijesti"

The present work shows the synthesis of nano-sized hybrid zeolitic imidazolate frameworks (ZIFs) with the rho topology based on a mixture of the linkers benzimidazole (bIm) and 4-methyl-5-imidazolecarboxaldehyde (4-m-5-ica). The hybrid ZIF was obtained by post-synthetic modification of ZIF-93 in a bIm solution. The use of different solvents, MeOH and N, N-dimethylacetamide (DMAc), and reaction times led to differences in the quantity of bIm incorporated to the framework, from 7.4 to 23 % according to solution-state NMR spectroscopy. XPS analysis showed that the mixture of linkers was also present at the surface of the particles. The inclusion of bIm to the ZIF-93 nanoparticles improved the thermal stability of the framework and also increased the hydrophobicity according to water adsorption results. N2 and CO2 adsorption experiments revealed that the hybrid material has an intermediate adsorption capacity, between those of ZIF-93 and ZIF-11. Finally, ZIF-93/11 hybrid materials were applied as fillers in polybenzimidazole (PBI) mixed matrix membranes (MMMs). These MMMs were used for H2/CO2 separation (at 180 °C) reaching values of 207 Barrer of H2 and a H2/CO2 selectivity of 7.7 that clearly surpassed the Robeson upper bound (corrected for this temperature)

Destruction of Dopaminergic Neurons in the Midbrain by 6-Hydroxydopamine Decreases Hippocampal Cell Proliferation in Rats: Reversal by Fluoxetine

Background Non-motor symptoms (e.g., depression, anxiety, and cognitive deficits) in patients with Parkinson disease (PD) precede the onset of the motor symptoms. Although these symptoms do not respond to pharmacological dopamine replacement therapy, their precise pathological mechanisms are currently unclear. The present study was undertaken to examine whether the unilateral 6-hydroxydopamine (6-OHDA) lesion to the substantia nigra pars compacta (SNc), which represents a model of long-term dopaminergic neurotoxicity, could affect cell proliferation in the adult rat brain. Furthermore, we examined the effects of the selective serotonin reuptake inhibitor (SSRI) fluoxetine and the selective noradrenaline reuptake inhibitor maprotiline on the reduction in cell proliferation in the subgranular zone (SGZ) by the unilateral 6-OHDA lesion. Methodology/Principal Findings A single unilateral injection of 6-OHDA into the rat SNc resulted in an almost complete loss of tyrosine hydroxylase (TH) immunoreactivity in the striatum and SNc, as well as in reductions of TH-positive cells and fibers in the ventral tegmental area (VTA). On the other hand, an injection of vehicle alone showed no overt change in TH immunoreactivity. A unilateral 6-OHDA lesion to SNc significantly decreased cell proliferation in the SGZ ipsilateral to the 6-OHDA lesion, but not in the contralateral SGZ or the subventricular zone (SVZ), of rats. Furthermore, subchronic (14 days) administration of fluoxetine (5 mg/kg/day), but not maprotiline significantly attenuated the reduction in cell proliferation in the SGZ by unilateral 6-OHDA lesion. Conclusions/Significance The present study suggests that cell proliferation in the SGZ of the dentate gyrus might be, in part, under dopaminergic control by SNc and VTA, and that subchronic administration of fluoxetine reversed the reduction in cell proliferation in the SGZ by 6-OHDA. Therefore, SSRIs such as fluoxetine might be potential therapeutic drugs for non-motor symptoms as well as motor symptoms in patients with PD, which might be associated with the reduction in cell proliferation in the SGZ

in keeping with the spirit of the albertine statute constitutionalisation of the national unification

This chapter deals with the difficult process of constitutionalisation which characterised Italian Unification. Constitutionalisation is a long-term phenomenon which had the purpose of giving constitutional forms to the Nation. The promulgation of the Albertine Statute is more the start than the arrival of this phenomenon. The focus of this investigation is, therefore, to study the Constitution through its evolution paying particular attention to the process of legal integration within the structures of the Albertine Statute and to the amendment mechanisms of the constitutional text. The preamble of the Albertine Statute speaks of «perpetual and irrevocable fundamental law». The word «perpetual» meant the prohibition of revoking constitutional concession, while the word «irrevocable» was intended as a pact between the Sovereign and the Nation. Over the years, very few were the changes to the letter of the Albertine Statute. The interpretation and the practice represented the most important mechanisms of constitutional change (implicit constitutional changes). A primary role was acknowledged to non-written norms. In this perspective, it may well be said that the Italian Constitution consisted in something more than the written text and dwelt in the spirit and not in the letter of the Albertine Statute

Can bias correction and statistical downscaling methods improve the skill of seasonal precipitation forecasts?

Statistical downscaling methods are popular post-processing tools which are widely used in many sectors to adapt the coarse-resolution biased outputs from global climate simulations to the regional-to-local scale typically required by users. They range from simple and pragmatic Bias Correction (BC) methods, which directly adjust the model outputs of interest (e.g. precipitation) according to the available local observations, to more complex Perfect Prognosis (PP) ones, which indirectly derive local predictions (e.g. precipitation) from appropriate upper-air large-scale model variables (predictors). Statistical downscaling methods have been extensively used and critically assessed in climate change applications; however, their advantages and limitations in seasonal forecasting are not well understood yet. In particular, a key problem in this context is whether they serve to improve the forecast quality/skill of raw model outputs beyond the adjustment of their systematic biases. In this paper we analyze this issue by applying two state-of-the-art BC and two PP methods to downscale precipitation from a multimodel seasonal hindcast in a challenging tropical region, the Philippines. To properly assess the potential added value beyond the reduction of model biases, we consider two validation scores which are not sensitive to changes in the mean (correlation and reliability categories). Our results show that, whereas BC methods maintain or worsen the skill of the raw model forecasts, PP methods can yield significant skill improvement (worsening) in cases for which the large-scale predictor variables considered are better (worse) predicted by the model than precipitation. For instance, PP methods are found to increase (decrease) model reliability in nearly 40% of the stations considered in boreal summer (autumn). Therefore, the choice of a convenient downscaling approach (either BC or PP) depends on the region and the season.This study was partially supported by the SPECS and EUPORIAS projects, funded by the European Commission through the Seventh Framework Programme for Research under grant agreements 308378 and 308291, respectively. JMG acknowledges partial support from the project MULTI-SDM (CGL2015-66583-R, MINECO/FEDER)