Green synthesis of MOF-based textile composites for the degradation of a chemical warfare agent simulant.

A green synthesis of UiO-66-NH2 embedded in chitosan and deposited on textiles has been investigated for the degradation of chemical warfare agents. This method requires no heating or use of toxic solvents. The composite synthesized presents an interesting efficiency in detoxifying common simulants of chemical warfare agents, such as DMNP. In parallel, resistance and permeability tests were also realized in order to confirm the suitability of the composites for further applications.

Electrochemical Properties of Silver Nanoparticles in Mesoporous Silica and Titania Films: Specific Behavior of Titania Composite.

Electrochemical behavior of silver nanoparticles in mesoporous oxides electrodes is investigated. Mesoporous SiO2 and TiO2 films deposited on FTO (fluorine-doped tin oxide) and containing Ag nanoparticles (NPs) are used as electrodes. The study of voltammetric curves (CVs) and the diffusion of Ag+ ions out of the films highlight the importance of the retention of Ag+ ions by the TiO2 films. By varying several factors such as the speed rate or the initial potential, we observe the existence of the two potentials' anodic peaks. These are explained by the nature of two silver NP populations created in two distinct areas in the film and with different size distributions, as shown by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. The size distributions of the two NP populations allow the position and shape of each of the oxidation peaks in the CVs to be adequately simulated.

Microwave-Assisted Synthesis of Porous Composites MOF-Textile for the Protection against Chemical and Nuclear Hazards.

Since the emergence of chemical, biological, radiological, and nuclear risks, significant efforts have been made to create efficient personal protection equipment. Recently, metal-organic framework (MOF) materials have emerged as new promising candidates for the capture and degradation of various threats, like chemical warfare agents (CWAs) or radioactive species. Herein, we report a new synthesis method of MOF-textile composites by microwave irradiation, with direct anchoring of MOFs on textiles. The resistance of the composite has been tested using normed abrasion measurements, and non-stable samples were optimized. The protection capacity of the MOF-textile composite has been tested against dimethyl 4-nitrophenyl phosphate, a common CWA simulant, showing short degradation half-life (30 min). Radiological/nuclear protection has also been tested through uranium uptake (up to 15 mg g-1 adsorbent) and the capture of Kr or Xe gas at 0.9 and 2.9 cm3/g, respectively.

Extrusion-Spheronization of UiO-66 and UiO-66_NH2 into Robust-Shaped Solids and Their Use for Gaseous Molecular Iodine, Xenon, and Krypton Adsorption.

The use of an extrusion-spheronization process was investigated to prepare robust and highly porous extrudates and granules starting from UiO-66 and UiO-66_NH2 metal-organic framework powders. As-produced materials were applied to the capture of gaseous iodine and the adsorption of xenon and krypton. In this study, biosourced chitosan and hydroxyethyl cellulose (HEC) are used as binders, added in low amounts (less than 5 wt % of the dried solids), as well as a colloidal silica as a co-binder when required. Characterizations of the final shaped materials reveal that most physicochemical properties are retained, except the textural properties, which are impacted by the process and the proportion of binders (BET surface area reduction from 5 to 33%). On the other hand, the mechanical resistance of the shaped materials toward compression is greatly improved by the presence of binders and their respective contents, from 0.5 N for binderless UiO-66 granules to 17 N for UiO-66@HEC granules. UiO-66_NH2-based granules demonstrated consequent iodine capture after 48 h, up to 527 mg/g, in line with the pristine UiO-66_NH2 powder (565 mg/g) and proportionally to the retaining BET surface area (-5% after shaping). Analogously, the shaped materials presented xenon and krypton sorption isotherms correlated to their BET surface area and high predicted xenon/krypton selectivity, from 7.1 to 9.0. Therefore, binder-aided extrusion-spheronization is an adapted method to produce shaped solids with adequate mechanical resistance and retained functional properties.

Electroactive Area from Porous Oxide Films Loaded with Silver Nanoparticles: Electrochemical and Electron Tomography Observations.

Electrochemical studies of nanomaterial-based electrodes have been widely developed for catalyst and energy-harvesting applications. The evolution of these electrodes over time and their efficiency have been extensively studied and analyzed in order to optimize their performance. However, the electrochemical responses of electrodes are rarely studied in terms of the position of the active species within these electrodes. In this paper, we highlight that the spatial location of silver nanoparticles (NPs) embedded inside semiconductive porous films, TiO2 or Fe2O3, is crucial for the electrochemical response. In fact, by using cycling voltammetry and electron tomography experiments, we show the existence of an "electroactive area", corresponding to a reduced thickness of the sample in close vicinity to a fluorine-doped tin oxide substrate where most of the electrochemical responses originate. Our results demonstrate that, for a film thickness of several hundred nanometers, only less than 30 nm close to the substrate responds electrochemically. However, cyclic voltammetry empties the electroactive area of silver NPs. Therefore, application of chronoamperometry coupled to irradiation allowed regeneration of this area thanks to an increased diffusion of silver species. In this paper, we also show the significant diffusion of silver species within the film during electrochemical experiments, a phenomenon even increased by irradiation. These results are therefore an important step that shows the importance of the localization of active species within a porous film and help in understanding and increasing the durability of nanomaterial-based electrodes.

Photoelectrochemical Behavior of Silver Nanoparticles inside Mesoporous Titania: Plasmon-Induced Charge Separation Effect.

The self-assembly block copolymer method was used to synthesize mesoporous titania films and silver nanoparticles (NPs) were grown inside the films. Such silver NPs-titania films are known for their multicolor photochromic properties due to a photo-oxidation reaction of silver in the presence of titania under light excitation which is attributed to a plasmon induced charge separation. Here, the photoelectrochemical properties of these composite films have been investigated at different light wavelengths and chemical environment in order to characterize the light-induced redox reactivity modifications. Cyclic voltammetry study shows that the Ag+ electro-reduction peak potential varies depending on the light irradiation, which determines the state of the silver nanoparticles complexed or not by titania.