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    Review and perspectives on the sustainability of organic aerogels
    Aerogels are exceptionally lightweight materials characterized by their high open porosity and remarkable specific surface area, currently used across a wide array of industrial sectors from construction to energy storage and have great potential for expanding their applicability and unlocking new market opportunities. Driven by global economic growth and an intensifying environmental crisis, there is a growing demand for engineering innovations that prioritize sustainability. Aerogels are well-positioned to support these sustainability efforts. Their unique properties make them ideal for energy-saving solutions, environmental remediation, and more efficient use of resources. As the demand for eco-conscious technologies rises, aerogels are poised to contribute significantly to the development of greener, more efficient products and processes across multiple industries. The sustainability of aerogel technology is crucial for the mid-to-long-term future, yet its current status has been scarcely reviewed in the literature. This Perspective explores and critically reviews significant advances on organic and hybrid aerogels in the current socioeconomic scenario, with selected case studies endorsing their contribution to the UN Sustainable Development Goals. It also identifies research gaps while proposing innovative strategies to enhance the sustainability of aerogel production through the application of circular economy principles. Key strategies discussed involve the fabrication of aerogels using eco-friendly sources, such as biopolymers derived from biorefinery processes or from waste materials. Additionally, this Perspective examines the development of methods for the reuse, recycling, and end-of-life management of aerogels, along with the implementation of more efficient processing routes. Ultimately, this work highlights the need for comprehensive assessments of aerogel sustainability through life cycle assessment (LCA) and evaluations of safety and toxicity. By addressing these critical aspects, the potential of aerogels to contribute to a more sustainable future appears highly favorable from both commercial and research perspectives, paving the way for a circular aerogel economy and providing a lasting impact to the society in which we live.
    Publicationtype: Review Article
      61  9
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    Whey protein isolate-based aerogels with improved hydration properties for food packaging applications
    (American Chemical Society (ACS), 2024-01-03) ; ; ; ;
    Ioannou, Dimosthenis
    In the present work, tannin-modified whey protein isolate (WPI/tannin) aerogels were synthesized, and their hydration properties were evaluated. The materials were prepared by introducing two different tannins (one hydrolyzable and one condensed) in the protein matrix via thermal-induced gelation of neutral or alkaline aqueous solutions (pH 7, 9, or 11) at 80 °C. WPI and WPI/tannin aerogels are nanostructured porous materials with high BET surface areas (216-353 m2 g-1). Subsequently, WPI and WPI/tannin aerogels were hydrophobized via silanization (with bis(trimethylsilyl)amine) in the gas phase (HWPI and HWPI/tannin aerogels). As a result of silanization, BET surface areas were reduced to 87-242 m2 g-1. The hydration properties of all aerogels were studied by measuring the water uptake and water contact angles. Pristine WPI aerogels absorbed high amounts of water (up to 4794% w/w in 24 h), swelled, and eventually disintegrated. WPI/tannin aerogels prepared with the condensed tannin absorbed more water (219-559% w/w) than those prepared with the hydrolyzable tannin (81-88% w/w). In any case, the water uptake was significantly lower compared with that of pristine WPI aerogels. After silanization, all aerogels absorbed much smaller amounts of water (39-84% w/w). The reduced water uptake was in agreement with the water contact angles, which were in the ranges 35-55° for WPI aerogels, 40-60° for WPI/tannin aerogels, 80-86° for HWPI aerogels, and 100-116° for HWPI/tannin aerogels. These results clearly indicate that both the introduction of tannin in the protein matrix and the silanization of the solid network are necessary to obtain water-stable WPI-based aerogels. There is an immense need for replacing the existing plastic-based food packaging with biobased and biodegradable materials. In this context, our results address the major disadvantage of most biobased materials (i.e., poor stability in aqueous environments) and render these new aerogels good candidates for food packaging applications.
    Publicationtype: Journal Article
      23
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    A greener approach to synthesizing metal-decorated carbogels from alginate for emerging technologies
    (Royal Society of Chemistry (RSC), 2023) ; ; ; ;
    Bermejo, María Dolores
    In the present work, a series of metal nanoparticle-decorated carbogels (M-DCs) was synthesized starting from beads of parent metal-crosslinked alginate aerogels (M-CAs), comprising Ca(II), Ni(II), Cu(II), Pd(II) and Pt(lV) ions, followed by pyrolysis under N2 atmosphere up to pyrolysis temperatures of TP = 600 ºC. The textural properties of M-CAs are found to depend on the crosslinking ion, yielding fibrous pore networks with high specific mesoporous volume and specific surface area SV (SV ~ 480 – 687 m2/g) for M-CAs crosslinked with hard cations, Ca(II), Ni(II) and Cu(II), and comparably loose networks with increased macroporosity and lower specific surface (SV ~ 240 – 270 m2/g) for Pd(II) and Pt(IV) crosslinked aerogels. The pyrolysis of M-CAs resulted in two simultaneously occurring processes: changes of the solid backbone and the growth of metal/metal oxide nanoparticles (NPs). The thermogravimetric analysis (TGA) showed a significant influence of the crosslinking cation on the decomposition mechanism and associated change of textural properties. Backscattered electron scanning electron microscopy imaging (SEM-BSE) and X-ray diffraction revealed that metal ions (molecularly dispersed in the parent aerogels) formed nanoparticles composed of elementary metals and metal oxides in varying ratios over the course of pyrolytic treatment. Increasing the TP led to in generally larger nanoparticles. The pyrolysis of the nickel-crosslinked aerogel (Ni-CA) preserved to a large extent the mesoporous structure and resulted in the evolution of fine (~ 14 nm) homogeneously dispersed Ni/NiO nanoparticles. Overall, this work presents a green approach for synthesizing metal-nanoparticle containing carbon materials, useful in emerging technologies related to heterogeneous catalysis, electrocatalysis among others.
    Publicationtype: Journal Article
      71  53
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    DEM-based approach for the modeling of gelation and its application to alginate
    (American Chemical Society (ACS), 2022-01-10) ; ; ; ;
    The gelation of biopolymers is of great interest in the material science community and has gained increasing relevance in the past few decades, especially in the context of aerogels lightweight open nanoporous materials. Understanding the underlying gel structure and influence of process parameters is of great importance to predict material properties such as mechanical strength. In order to improve understanding of the gelation mechanism in aqueous solution, this work presents a novel approach based on the discrete element method for the mesoscale for modeling gelation of hydrogels, similarly to an extremely coarse-grained molecular dynamics (MD) approach. For this, polymer chains are abstracted as dimer units connected by flexible bonds and interactions between units and with the environment, that is, diffusion in implicit water, are described. The model is based on Langevin dynamics and includes an implicit probabilistic ion model to capture the effects of ion availability during ion-mediated gelation. The model components are fully derived and parameterized using literature data and theoretical considerations based on a simplified representation of atomistic processes. The presented model enables investigations of the higher-scale network formation during gelation on the micrometer and millisecond scale, which are beyond classical modeling approaches such as MD. As a model system, calcium-mediated alginate gelation is investigated including the influence of ion concentration, polymer composition, polymer concentration, and molecular weight. The model is verified against numerous literature data as well as own experimental results for the corresponding Ca-alginate hydrogels using nitrogen porosimetry, NMR cryoporometry, and small-angle neutron scattering. The model reproduces both bundle size and pore size distribution in a reasonable agreement with the experiments. Overall, the modeling approach paves the way to physically motivated design of alginate gels.
    Publicationtype: Journal Article
    Scopus© Citations 9  196  1442
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    False morphology of aerogels caused by gold coating for SEM imaging
    (Multidisciplinary Digital Publishing Institute (MDPI), 2021-02-02) ; ; ; ;
    The imaging of non-conducting materials by scanning electron microscopy (SEM) is most often performed after depositing few nanometers thick conductive layers on the samples. It is shown in this work, that even a 5 nm thick sputtered gold layer can dramatically alter the morphology and the surface structure of many different types of aerogels. Silica, polyimide, polyamide, calcium-alginate and cellulose aerogels were imaged in their pristine forms and after gold sputtering utilizing low voltage scanning electron microscopy (LVSEM) in order to reduce charging effects. The morphological features seen in the SEM images of the pristine samples are in excellent agreement with the structural parameters of the aerogels measured by nitrogen adsorption-desorption porosimetry. In contrast, the morphologies of the sputter coated samples are significantly distorted and feature nanostructured gold. These findings point out that extra care should be taken in order to ensure that gold sputtering does not cause morphological artifacts. Otherwise, the application of low voltage scanning electron microscopy even yields high resolution images of pristine non-conducting aerogels.
    Publicationtype: Journal Article
    Scopus© Citations 25  115  383
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    Mechanism of Hydration and Hydration Induced Structural Changes of Calcium Alginate Aerogel
    The most relevant properties of polysaccharide aerogels in practical applications are determined by their microstructures. Hydration has a dominant role in altering the microstructures of these hydrophilic porous materials. To understand the hydration induced structural changes of monolithic Ca-alginate aerogel, produced by drying fully cross-linked gels with supercritical CO2, the aerogel was gradually hydrated and characterized at different states of hydration by small-angle neutron scattering (SANS), liquid-state nuclear magnetic resonance (NMR) spectroscopy, and magic angle spinning (MAS) NMR spectroscopy. First, the incorporation of structural water and the formation of an extensive hydration sphere mobilize the Ca-alginate macromolecules and induce the rearrangement of the dry-state tertiary and quaternary structures. The primary fibrils of the original aerogel backbone form hydrated fibers and fascicles, resulting in the significant increase of pore size, the smoothing of the nanostructured surface, and the increase of the fractal dimension of the matrix. Because of the formation of these new superstructures in the hydrated backbone, the stiffness and the compressive strength of the aerogel significantly increase compared to its dry-state properties. Further elevation of the water content of the aerogel results in a critical hydration state. The Ca-alginate fibers of the backbone disintegrate into well-hydrated chains, which eventually form a quasi-homogeneous hydrogel-like network. Consequently, the porous structure collapses and the well-defined solid backbone ceases to exist. Even in this hydrogel-like state, the macroscopic integrity of the Ca-alginate monolith is intact. The postulated mechanism accounts for the modification of the macroscopic properties of Ca-alginate aerogel in relation to both humid and aqueous environments.
    Publicationtype: Journal Article
    Scopus© Citations 21  78
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    A redox strategy to tailor the release properties of Fe(III)-alginate aerogels for oral drug delivery
    Iron(III)-crosslinked alginate aerogel beads (d = 3-5 mm) were prepared and loaded with ibuprofen by using the technique of adsorptive deposition from supercritical CO2. Additional formulations were prepared where the aerogels were co-impregnated by ibuprofen and ascorbic acid. The release of ibuprofen from the Fe(III)-alginate is much faster in pH = 7.4 (PBS) than in pH = 2.0 (HCl), which can be explained by the faster dissolution and higher swelling of the alginate matrix in PBS. By decreasing the size of the beads and using a higher G content alginate the release rate could be slightly increased. A marked acceleration of drug release was achieved in both HCl and PBS by incorporating ascorbic acid into the Fe(III)-alginate aerogel preparations. The explanation is that in aqueous media ascorbic acid in situ reduces the crosslinking Fe(III) to Fe(II). The latter does not interact strongly with alginate, which promotes the hydration of the chains, thus the erosion and dissolution of the carrier matrix.
    Publicationtype: Journal Article
      140