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Sulim, O., R. Ribeiro, I. Esteves, C. Antunes, A. Garate, P. Duarte, I. Ferreira, J. Mota, and M. Plaza, Design of structured adsorbents for aplications in gas adsorption processes - Conventional shaping vs 3D-Printed formulation, , 5-10 March, 2017. Abstract

Microporous materials highly activated and with potential to be used as adsorbents in many applications for gas
separation/purification are usually available as powders. These solids usually have a great and reversible gas
uptake, high gas selectivity, good chemical and thermal stability, but are unsuitable to be used in gas adsorption
processes, such as Pressure Swing Adsorption (PSA) or Simulated Moving Bed (SMB).
Zeolites, carbons and more recently metal-organic frameworks (MOFs) are examples of those materials. Their
use in adsorption-based processes are dependent of their upgrading from powders (micrometer scale) to
particles (pellets, spheres or granules at millimeter scale). This would overcome large pressure drops and
consequent energy consumptions when packing adsorbent columns in those processes. Thus, shaping
adsorbents is an important step to use them in industry, although it greatly affects their capacity and selectivity
towards a specific gas separation.
In this work, we explore techniques to shape powdered adsorbents, followed by their textural and mechanical
characterizations, and the study of their adsorption properties towards the main components of post-combustion
flues gases (CO2 and N2). Materials densification is proposed by employing two approaches:
- Conventional shaping through binderless mechanical compression and binder-containing extrusion; and
- Formulation by 3D printing (or additive manufacturing) to produce packed bed morphologies that
precisely replicate computer aided design (CAD) models.
Porous separation media are important for fluid-solid contacting in many unit operations, including adsorption.
Due to practical limitations, media particles are typically packed randomly into a column in a shaped form,
allowing fluid to flow through the interstitial voids. Key to the effectiveness of packed columns are the flowrelated properties of mass transfer, fluid distribution and dispersion, and back pressure, which in turn depend
upon packing geometry. Until now, no alternative was found to overcome this limitation and have optimal
ordered packing arrangements at the micron scale. 3D-Printing (or additive manufacturing) brings a wide range
of benefits that traditional methods of manufacturing or prototyping simply cannot. With this approach, complex
ordered geometries, that are not possible by conventional extrusion, can be designed and printed for a porous
media, being the equipment resolution the only limiting step to overcome.
The effect of parameters like compression force, particle sieving, binder nature, binder/adsorbent ratio were
firstly studied using conventional shaping techniques, as a basis for the consequent development of 3D-printed
formulations. The structured samples are then characterized and adsorption equilibria studies are performed on
them to evaluate their performance as media for gas adsorption separation processes. A volumetric/manometric
adsorption unit built in-house was used for this purpose. Relevant experimental data is obtained, which allows to
conclude that 3D-printed media can be an alternative porous media for application in gas adsorption processes.

Strohmeier, P., C. Honnet, H. Pernet-Wilson, M. Teyssier, B. Fruchard, A. C. Baptista, and J. Steimle, "PolySense: How to Make Electrically Functional Textiles", CHI Conference on Human Factors in Computing Systems , 2020.
Sousa, D. M., L. Cerqueira, A. Marques, G. Gaspar, J. C. Lima, and I. Ferreira, "Facile Microwave-assisted Synthesis Manganese Doped Zinc Sulfide Nanoparticles", Scientific Reports, vol. 8, pp. 15992, 2018.
Sousa, D. M., J. C. Lima, and I. Ferreira, "Image Recording and Processing Chemical Synthesis: Method Description and Demonstration", Chemistry‐Methods, vol. 1, pp. 157-161, 2021.
Sousa, D. M., W. Chiappim, J. P. Leitão, J. C. Lima, and I. Ferreira, "Microwave synthesis of silver sulfide and silver nanoparticles: light and time influence", ACS omega, vol. 5, pp. 12877-12881, 2020.
Sousa, D. M., J. C. Lima, and I. Ferreira, "Synthesis of Cadmium Selenide Quantum Dots, Using 2, 2‐Bipyridine as a Capping and Phase Transfer Agent", ChemistrySelect, vol. 2, issue 3, pp. 1271-1274, 2017. AbstractDOI

Cadmium selenide quantum dots (CdSe QDs), were synthesized by one‐pot or water‐to‐organic phase transfer and capped with molten 2,2′‐bipyridine (bipy). The obtained CdSe QDs by the two‐step procedure, reveal average sizes of 2 nm while the one‐pot are mixed with secondary salt products and bipy and are undetectable by TEM. However the absorption peak of both CdSe QDs was at 425 nm and the emission band is centered at 535 nm, with a band width at half height of 77 nm, when excited with 425 nm light. The two‐step CdSe QDs synthesis has the great advantage of capping the CdSe QDs with bipy, forming a solid phase, which is easily stored and dispersed in most of the organic solvents. On the other hand, the one‐pot procedure requires an extra step to remove the secondary products.

Soares, P. I. P., D. Machado, C. Laia, L. C. J. Pereira, J. T. Coutinho, I. M. M. Ferreira, C. M. M. Novo, and J. P. Borges, "Thermal and magnetic properties of chitosan-iron oxide nanoparticles", Carbohydr Polym, vol. 149, pp. 382-390, 2016. AbstractDOI

Chitosan is a biopolymer widely used for biomedical applications such as drug delivery systems, wound healing, and tissue engineering. Chitosan can be used as coating for other types of materials such as iron oxide nanoparticles, improving its biocompatibility while extending its range of applications.

In this work iron oxide nanoparticles (Fe3O4 NPs) produced by chemical precipitation and thermal decomposition and coated with chitosan with different molecular weights were studied. Basic characterization on bare and chitosan-Fe3O4 NPs was performed demonstrating that chitosan does not affect the crystallinity, chemical composition, and superparamagnetic properties of the Fe3O4 NPs, and also the incorporation of Fe3O4 NPs into chitosan nanoparticles increases the later hydrodynamic diameter without compromising its physical and chemical properties. The nano-composite was tested for magnetic hyperthermia by applying an alternating current magnetic field to the samples demonstrating that the heating ability of the Fe3O4 NPs was not significantly affected by chitosan.

Soares, P. I. P., A. M. R. Alves, L. C. J. Pereira, J. T. Coutinho, I. M. M. Ferreira, C. M. M. Novo, and J. P. M. R. Borges, "Effects of surfactants on the magnetic properties of iron oxide colloids", J. Colloid Interface Sci., vol. 419, pp. 46-51, 2014. AbstractDOI

Iron oxide nanoparticles are having been extensively investigated for several biomedical applications such as hyperthermia and magnetic resonance imaging. However, one of the biggest problems of these nanoparticles is their aggregation.

Taking this into account, in this study the influence of three different surfactants (oleic acid, sodium citrate and Triton X-100) each one with various concentrations in the colloidal solutions stability was analyzed by using a rapid and facile method, the variation in the optical absorbance along time.

The synthesized nanoparticles through chemical precipitation showed an average size of 9 nm and a narrow size distribution. X-ray diffraction pattern and Fourier Transform Infrared analysis confirmed the presence of pure magnetite. SQUID measurements showed superparamagnetic properties with a blocking temperature around 155 K. In addition it was observed that neither sodium citrate nor Triton X-100 influences the magnetic properties of the nanoparticles. On the other hand, oleic acid in a concentration of 64 mM decreases the saturation magnetization from 67 to 45 emu/g. Oleic acid exhibits a good performance as stabilizer of the iron oxide nanoparticles in an aqueous solution for 24 h, for concentrations that lead to the formation of the double layer.

Soares, P. I. P., A. I. Sousa, I. M. M. Ferreira, C. M. M. Novo, and J. P. Borges, "Towards the development of multifunctional chitosan-based iron oxide nanoparticles: Optimization and modelling of doxorubicin release", Carbohydr Polym, vol. 153, pp. 212-221, 2016. AbstractDOI

In the present work composite nanoparticles with a magnetic core and a chitosan-based shell were produced as drug delivery systems for doxorubicin (DOX). The results show that composite nanoparticles with a hydrodynamic diameter within the nanometric range are able to encapsulate more DOX than polymeric nanoparticles alone corresponding also to a higher drug release. Moreover the synthesis method of the iron oxide nanoparticles influences the total amount of DOX released and a high content of iron oxide nanoparticles inhibits DOX release. The modelling of the experimental results revealed a release mechanism dominated by Fickian diffusion.

Soares, Í., J. Faria, A. Marques, I. A. C. Ribeiro, C. Baleizão, A. Bettencourt, I. Ferreira, and A. C. Baptista, "Drug Delivery from PCL/Chitosan Multilayer Coatings for Metallic Implants", ACS omega, vol. 7, pp. 23096-23106, 2022.