A 3D Printed Membrane Reactor System for Electrochemical CO2 Conversion.

Nowadays, CO2 electroreduction is gaining special interest as achieving net zero CO2 emissions is not going to be enough to avoid or mitigate the negative effects of climate change. However, the cost of CO2 electroreduction is still very high because of the low efficiency of conversion (around 20%). Therefore, it is necessary to optimize the reaction conditions. Thus, a miniaturized novel membrane reactor was designed and manufactured in this study, with a shorter distance between the electrodes and a reduced volume, compared with CNC-manufactured reactors, using novel stereolithography-based 3D printing. The reduced distance between the two electrodes reduced the electrical resistance and therefore lowered the overpotential necessary to trigger the reaction from -1.6 V to -1.2 V, increasing the efficiency. In addition, the reduction in the volume of the reactor increased the catalyst area/volume ratio, which also boosted the concentration of the products (from FE 18% to FE 21%), allowing their better identification. Furthermore, the smaller volume and reduced complexity of the reactor also improved the testing capacity and decreased the cost of experimentation. The novel miniaturized reactor can help researchers to perform more experiments in a cost/time-effective way, facilitating the optimization of the reaction conditions.

Supported Imidazolium-Based Ionic Liquids on a Polysulfone Matrix for Enhanced CO2 Capture.

The present work demonstrates the potential for improved CO2 capture capabilities of ionic liquids (ILs) by supporting them on a polysulfone polymeric matrix. CO2 is one of the main gases responsible for the greenhouse effect and is a focus of The European Commission, which committed to diminishing its emission to 55% by 2023. Various ILs based on combinations of 1-butyl-3-methyl- imidazolium cations and different anions (BMI·X) were synthesized and supported on a polysulfone porous membrane. The influence of the membrane structure and the nature of ILs on the CO2 capture abilities were investigated. It was found that the membrane's internal morphology and its surface characteristics influence its ILs sorption capacity and CO2 solubility. In most of the studied configurations, supporting ILs on porous structures increased their contact surface and gas adsorption compared to the bulk ILs. The phenomenon was strongly pronounced in the case of ILs of high viscosity, where supporting them on porous structures resulted in a CO2 solubility value increase of 10×. Finally, the highest CO2 solubility value (0.24 molCO2/molIL) was obtained with membranes bearing supported ILs containing dicarboxylate anion (BMI.MAL).

MEA Preparation for Direct Formate/Formic Acid Fuel Cell-Comparison of Palladium Black and Palladium Supported on Activated Carbon Performance on Power Generation in Passive Fuel Cell.

Membrane electrode assemblies (MEAs) with palladium catalysts were successfully prepared by using a home-made manual pressing system with Nafion glue application that contributed to a decrease of additional energy consumption. The catalyst coated membranes were prepared with supported palladium on activated carbon (PdC) and unsupported palladium black (PdB) for comparison. The performance of passive, air breathing, functioning under ambient conditions and with low concentration (1 M) formate/formic acid fuel cell was evaluated. Based on polarization curves, the best result was obtained with carbon supported catalyst and HCOOK fuel, achieving 21.01 mW/mgPd. Still, constant current discharge with PdC showed an energy generation efficiency of 14% with HCOOH over 3% with HCOOK caused by lower potassium ion conductivity and its permeability through the proton exchange membrane. The faradic efficiency of conversion in the cell is equal to the overall energy efficiency and makes the cell self-sufficient.

Contrasting Photo-Switching Rates in Azobenzene Derivatives: How the Nature of the Substituent Plays a Role.

A molecular design approach was used to create asymmetrical visible light-triggered azo-derivatives that can be good candidates for polymer functionalization. The specific electron-donor substituted molecules were characterized and studied by means of NMR analyses and UV-visible spectroscopy, comparing the results with Time Dependent Density Functional (TD-DFT) calculations. A slow rate of isomerization (ki = 1.5 × 10-4 s-1) was discovered for 4-((2-hydroxy-5methylphenyl) diazenyl)-3-methoxybenzoic acid (AZO1). By methylating this moiety, it was possible to unlock the isomerization mechanism for the second molecule, methyl 3-methoxy-4-((2-methoxy-5-methylphenyl) diazenyl)benzoate (AZO2), reaching promising isomerization rates with visible light irradiation in different solvents. It was discovered that this rate was heightened by one order of magnitude (ki = 3.1 × 10-3 s-1) for AZO2. A computational analysis using density functional (DFT/PBE0) and wavefunction (QD-NEVPT2) methodologies provided insight into the photodynamics of these systems. Both molecules require excitation to the second (S2) excited state situated in the visible region to initiate the isomerization. Two classic mechanisms were considered, namely rotation and inversion, with the former being energetically more favorable. These azo-derivatives show potential that paves the way for future applications as building blocks of functional polymers. Likewise, they could be really effective for the modification of existing commercial polymers, thus transferring their stimuli responsive properties to polymeric bulky structures, converting them into smart materials.

Stability and anti-proliferative properties of biologically active compounds extracted from Cistus L. after sterilization treatments.

The growing interest of oncologists in natural compounds such as polyphenols and flavonoids is encouraging the development of innovative and efficient carriers for the delivery of those drugs. This study examines carboxymethyl chitosan-based microcapsules created by spray drying as a method for delivering biologically active compounds isolated from the Cistus herb. Effects of sterilization and encapsulation on the polyphenol and flavonoid content of Cistus extract were investigated to optimize the production process. Furthermore, in vitro studies were carried out to examine the anticancer properties of sterilized polyphenols and flavonoids on glioblastoma cells isolated from oncological patients. Acquired results show high anticancer potential towards glioblastoma as well as low cytotoxicity towards non-cancer cell lines by the substances in question. Steam sterilization is shown to affect the content of biologically active compounds the least. We demonstrate that the investigated form of drug encapsulation is both efficient and potentially possible to scale up from the viewpoint of the pharmaceutical industry.

Encapsulation for Cancer Therapy.

The current rapid advancement of numerous nanotechnology tools is being employed in treatment of many terminal diseases such as cancer. Nanocapsules (NCs) containing an anti-cancer drug offer a very promising alternative to conventional treatments, mostly due to their targeted delivery and precise action, and thereby they can be used in distinct applications: as biosensors or in medical imaging, allowing for cancer detection as well as agents/carriers in targeted drug delivery. The possibility of using different systems-inorganic nanoparticles, dendrimers, proteins, polymeric micelles, liposomes, carbon nanotubes (CNTs), quantum dots (QDs), biopolymeric nanoparticles and their combinations-offers multiple benefits to early cancer detection as well as controlled drug delivery to specific locations. This review focused on the key and recent progress in the encapsulation of anticancer drugs that include methods of preparation, drug loading and drug release mechanism on the presented nanosystems. Furthermore, the future directions in applications of various nanoparticles are highlighted.

Polymer Blends for Improved CO2 Capture Membranes.

We investigated the possibility of improving the performance of polysulfone (PSf) membranes to be used in carbon dioxide capture devices by blending PSf with a commercial polyethylene imine, Lupasol G20, previously modified with benzoyl chloride (mG20). Additive amount ranged between 2 and 20 wt %. Membranes based on these blends were prepared by phase inversion precipitation and exhibited different morphologies with respect to neat PSf. Surface roughness, water contact angles, and water uptake increased with mG20 content. Mass transfer coefficient was also increased for both N2 and CO2; however, this effect was more evident for carbon dioxide. Carbon dioxide absorption performance of composite membranes was evaluated for potassium hydroxide solution in a flat sheet membrane contactor (FSMC) in cross flow module at different liquid flow rates. We found that, at the lowest flow rate, membranes exhibit a very similar behaviour to neat PSf; nevertheless, significant differences can be found at higher flow rates. In particular, the membranes with 2 and 5 wt % additive behave more efficiently than neat PSf. In contrast, 10 and 20 wt % additive content has an adverse effect on CO2 capture when compared with neat PSf. In the former case, a combination of additive chemical affinity to CO2 and membrane porosity can be claimed; in the latter case, the remarkably higher wettability and water uptake could determine membrane clogging and consequent loss of efficiency in the capture device.

Atmospheric CO2 capture for the artificial photosynthetic system.

The aim of these studies is to evaluate the ambient CO2 capture abilities of the membrane contactor system in the same conditions as leafs, such as ambient temperature, pressure and low CO2 concentration, where the only driving force is the concentration gradient. The polysulfone membrane employed was made by a phase inversion process and characterized by ESEM micrographs which were used to determine the thickness, asymmetry and pore size. Besides, the porosity of the membrane was measured from the membrane and polysulfone density correlation and the hydrophobicity was analyzed by contact angle measurements. Moreover, the compatibility of membrane and absorbent was evaluated, in order to exclude wetting issues by meaning of swelling, dynamic contact angle and AFM analysis. The prepared membranes were introduced into a cross flow module and used as contactors between CO2 and the absorbing media, a potassium hydroxide solution. The influence of the membrane thickness, absorbent stirring rate, solution pH and absorption time on CO2 capture were evaluated. Absorbent solution stirring rate showed no statistically significant influence on absorption. We observed a non-linear correlation between the capture rate and the increase of absorbent solution pH as well as absorption time. The results showed that the efficiency of our CO2 capture system is similar to stomatal carbon dioxide assimilation rate, achieving stable value of 20µmol/m2·s after 1h of experiment.

Preparation, characterization and gas permeation investigation of resorcinol-formaldehyde polymer or carbon xerogels/tubular ceramic composites.

New very stable composites prepared by deposition of resorcinol-formaldehyde polymer (RF-) or carbon (C-) xerogels into walls of commercial porous tubular ceramics (TiO2-ZrO2 and alphaAl2O3-gammaAl203) were obtained by a sol-gel process followed by a drying and a pyrolytic (only for C-xerogel/ceramic composites) step. They were characterized by nitrogen adsorption-desorption, SEM and XRD, and tested for gas (H2, CH4, CO2 and CO) separation applications. Additional morpho-structural information about the open-interconnected ultramicropore structure of composites was found by gas permeation investigation. Interesting results for H2 permeance was obtained especially for RF-polymer/ceramic composites respecting Knudsen diffusion mechanism of gas permeance: H2 > CH4 > CO > CO2. The coexistence of Knudsen and surface diffusion mechanisms were confirmed.

Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses.

Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.

Light-induced switching of the wettability of novel asymmetrical poly(vinyl alcohol)-co-ethylene membranes blended with azobenzene polymers.

Novel composite asymmetrical membranes based on poly(vinyl alcohol)-co-ethylene (EVAL) as the host material and new polyethers that contain azobenzene moieties in the side chain were prepared by dry-cast phase inversion after dissolving the azo polymers in tetrahydrofuran and EVAL in dimethylsulfoxide and subsequently mixing the resulting solutions. By taking advantage of the proper temperature variation in the oven used for solvent evaporation, asymmetrical membranes that exhibited a dense, crystalline layer on the bottom and a porous, mainly amorphous layer on the top were obtained. Remarkable changes in the surface morphology and the contact angle with water were observed on the top surfaces of the composite membranes. This was ascribed not only to the enhanced concentration of azo polymer on the top surface but mostly to a conformational change in EVAL induced by the photoisomerization of the guest azo groups, as shown by HRMAS (1)H NMR. The morphological and structural changes in EVAL could be reversed on exposing the membrane to visible light for 24 h.