Thermogravimetric Analysis of Moisture in Natural and Thermally Treated Clay Materials.

Clays are a class of porous materials; their surfaces are naturally covered by moisture. Weak thermal treatment may be considered practical to remove the water molecules, changing the surface properties and making the micro- and/or mesoporosities accessible to interact with other molecules. Herein, a modulated thermogravimetric analysis (MTGA) study of the moisture behavior on the structures of five, both fibrous and laminar, clay minerals is reported. The effect of the thermal treatment at 150 °C, which provokes the release of weakly adsorbed water molecules, was also investigated. The activation energies for the removal of the adsorbed water (Ea) were calculated, and they were found to be higher, namely, from 160 to 190 kJ mol-1, for fibrous clay minerals compared to lamellar structures, ranging in this latter case from 80 to 100 kJ mol-1. The thermal treatment enhances the rehydration in Na-montmorillonite, stevensite, and sepiolite structures with a decrease in the energy required to remove it, while Ea increases significantly in palygorskite (from 164 to 273 kJ mol-1). As a proof of concept, the MTGA results are statistically correlated, together with a full characterization of the physico-chemical properties of the five clay minerals, with the adsorption of two molecules, i.e., aflatoxin B1 (AFB1) and ß-carotene. Herein, the amount of adsorbed molecules ranges from 12 to 97% for the former and from 22 to 35% for the latter, depending on the particular clay. The Ea was correlated with AFB1 adsorption with a Spearman score of -0.9. When the adsorbed water is forcibly removed, e.g., under vacuum conditions and high temperatures, the structure becomes the most important, decreasing the Spearman score between ß-carotene and Ea to -0.6.

Machine learning-aided design of composite mycotoxin detoxifier material for animal feed.

The development of food and feed additives involves the design of materials with specific properties that enable the desired function while minimizing the adverse effects related with their interference with the concurrent complex biochemistry of the living organisms. Often, the development process is heavily dependent on costly and time-consuming in vitro and in vivo experiments. Herein, we present an approach to design clay-based composite materials for mycotoxin removal from animal feed. The approach can accommodate various material compositions and different toxin molecules. With application of machine learning trained on in vitro results of mycotoxin adsorption-desorption in the gastrointestinal tract, we have searched the space of possible composite material compositions to identify formulations with high removal capacity and gaining insights into their mode of action. An in vivo toxicokinetic study, based on the detection of biomarkers for mycotoxin-exposure in broilers, validated our findings by observing a significant reduction in systemic exposure to the challenging to be removed mycotoxin, i.e., deoxynivalenol (DON), when the optimal detoxifier is administrated to the animals. A mean reduction of 32% in the area under the plasma concentration-time curve of DON-sulphate was seen in the DON + detoxifier group compared to the DON group (P = 0.010).

Sepiolite-Hydrogels: Synthesis by Ultrasound Irradiation and Their Use for the Preparation of Functional Clay-Based Nanoarchitectured Materials.

Sepiolite and palygorskite fibrous clay minerals are 1D silicates featuring unique textural and structural characteristics useful in diverse applications, and in particular as rheological additives. Here we report on the ability of grinded sepiolite to generate highly viscous and stable hydrogels by sonomechanical irradiation (ultrasounds). Adequate drying of such hydrogels leads to low-density xerogels that show extensive fiber disaggregation compared to the starting sepiolite-whose fibers are agglomerated as bundles. Upon re-dispersion in water under high-speed shear, these xerogels show comparable rheological properties to commercially available defibrillated sepiolite products, resulting in high viscosity hydrogels that minimize syneresis. These colloidal systems are thus very interesting as they can be used to stabilize many diverse compounds as well as nano-/micro-particles, leading to the production of a large variety of composites and nano/micro-architectured solids. In this context, we report here various examples showing how colloidal routes based on sepiolite hydrogels can be used to obtain new heterostructured functional materials, based on their assembly to solids of diverse topology and composition such as 2D and 1D kaolinite and halloysite aluminosilicates, as well as to the 2D synthetic Mg,Al-layered double hydroxides (LDH).

Machine-learning-accelerated multimodal characterization and multiobjective design optimization of natural porous materials.

Natural porous materials such as nanoporous clays are used as green and low-cost adsorbents and catalysts. The key factors determining their performance in these applications are the pore morphology and surface activity, which are typically represented by properties such as specific surface area, pore volume, micropore content and pH. The latter may be modified and tuned to specific applications through material processing and/or chemical treatment. Characterization of the material, raw or processed, is typically performed experimentally, which can become costly especially in the context of tuning of the properties towards specific application requirements and needing numerous experiments. In this work, we present an application of tree-based machine learning methods trained on experimental datasets to accelerate the characterization of natural porous materials. The resulting models allow reliable prediction of the outcomes of experimental characterization of processed materials (R 2 from 0.78 to 0.99) as well as identification of key factors contributing to those properties through feature importance analysis. Furthermore, the high throughput of the models enables exploration of processing parameter-property correlations and multiobjective optimization of prototype materials towards specific applications. We have applied these methodologies to pinpoint and rationalize optimal processing conditions for clays exploitable in acid catalysis. One of such identified materials was synthesized and tested revealing appreciable acid character improvement with respect to the pristine material. Specifically, it achieved 79% removal of chlorophyll-a in acid catalyzed degradation.

Functional biohybrid materials based on halloysite, sepiolite and cellulose nanofibers for health applications.

Biohybrid materials were prepared by co-assembling the three following components: nanotubular halloysite, microfibrous sepiolite, and cellulose nanofibers dispersed in water, in order to exploit the most salient features of each individual component and to render homogeneous, flexible, yet strong films. Indeed, the incorporation of halloysite improves the mechanical performance of the resulting hybrid nanopapers and the assembly of the three components modifies the surface features concerning wetting properties compared to pristine materials, so that the main characteristics of the resulting materials become tunable with regard to certain properties. Owing to their hierarchical porosity together with their diverse surface characteristics, these hybrids can be used in diverse biomedical/pharmaceutical applications. Herein, for instance, loading with two model drugs, salicylic acid and ibuprofen, allows controlled and sustained release as deduced from antimicrobial assays, opening a versatile path for developing other related organic-inorganic materials of potential interest in diverse application fields.

Multicomponent bionanocomposites based on clay nanoarchitectures for electrochemical devices.

Based on the unique ability of defibrillated sepiolite (SEP) to form stable and homogeneous colloidal dispersions of diverse types of nanoparticles in aqueous media under ultrasonication, multicomponent conductive nanoarchitectured materials integrating halloysite nanotubes (HNTs), graphene nanoplatelets (GNPs) and chitosan (CHI) have been developed. The resulting nanohybrid suspensions could be easily formed into films or foams, where each individual component plays a critical role in the biocomposite: HNTs act as nanocontainers for bioactive species, GNPs provide electrical conductivity (enhanced by doping with MWCNTs) and, the CHI polymer matrix introduces mechanical and membrane properties that are of key significance for the development of electrochemical devices. The resulting characteristics allow for a possible application of these active elements as integrated multicomponent materials for advanced electrochemical devices such as biosensors and enzymatic biofuel cells. This strategy can be regarded as an "a la carte" menu, where the selection of the nanocomponents exhibiting different properties will determine a functional set of predetermined utility with SEP maintaining stable colloidal dispersions of different nanoparticles and polymers in water.