The use of composite solid-state electrolytes (CSEs) in Li-ion batteries presents a promising future for a new generation of solid-state battery technology. These composites address current limitations like poor room temperature ionic conductivity, low mechanical strength, and unstable interfaces. In this study, a NASICON-type Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) ceramic was prepared using a cold sintering process (CSP), incorporating LATP, poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). This three-component CSE demonstrated reduced sintering temperature, energy, time, and operational costs compared to traditional methods. The LATP-based pellet achieved high density and a prismatic structure without impurities. The addition of a polymeric binder and an ionic liquid improved the nanostructuration, dispersion, mechanical properties, and relative density of the CSEs. Small-angle neutron scattering revealed nanostructuration changes, decreasing air pore size. Notably, room temperature ionic conductivities between 10-4 - 10-3 S cm-1 were achieved, with a maximum conductivity of 7.02 x 10-3 S cm-1 and lithium-transference number of 0.35 for the sample with 99 wt.% LATP and 1 wt.% polymeric binder. Additionally, a room temperature discharge capacity of 141 mAh.g-1 at C/10 rate was attained after 50 cycles, validating this three-component structure as a promising platform for high-performance CSEs in solid-state batteries.

A porous, photocatalytically active, and water-stable composite filter has been developed based on MIL-125-NH2, a Titanium-based Metal-Organic Framework (MOF) and chitin polymeric scaffold. In order to tune the structure and functional properties of the CH/MOF composites, the loading degree of the MOF within the polymer was systematically varied. The composite material optimal performance was achieved with a 10% wt/wt loading of MIL-125-NH2 into the chitin scaffold. This composite material was able to capture and photodegrade Trimethoprim (TMP) under acid and alkaline conditions with outstanding efficiency (82% within 180min), as well as in waters collected from different geographical locations nearby Buenos Aires that were spiked with TMP. Furthermore, the chemical stability of MIL-125-NH2 is significantly improved when incorporated into the chitin scaffold, maintaining its structural integrity even after four cycles of reactivation and reusability. The study outlines the experimental procedures for synthesizing MIL-125-NH2, preparing chitin hydrogel and nanostructured composites, and details on the adsorption and photocatalysis experiments. The practical application of our approach can be further expanded to prevent degradation during gas or liquid adsorption processes of hydrolytically unstable MOFs.

Two of the main factors controlling the activity and selectivity of metal sites within MOF-like copper metalloenzymes are: (i) their coordination environments, and (ii) the number and connectivity of metal ions at the active site (i.e., nuclearity).

Incorporation of ionic liquids into ZIF-8 pores to obtain solid-ionic conductors that work as active layers in printed gas capacitive sensors to detect water and non-methane volatile organic vapours.

The presence of arsenic as neutral arsenite and oxoanionic arsenate species are a worldwide issue that requires an effective remediation technology capable to remove both AsIII and AsV from water. In this research we propose the assembly of a membrane build up from chitosan/pectin (CHIPEC) composite biopolymer and the UiO-66-NH2 porous and photo-active metal-organic framework. CHIPEC@UiO-66-NH2 membrane integrates porosity, adsorptive capacity, and activity to photo-oxidize and adsorb AsIII and AsV species. Nanometric-sized UiO-66NH2 was synthetized and homogeneously distributed within the CHIPEC matrix, achieving a composite membrane with optical physico-chemical and optical properties (band gap of 2.91 eV) suitable to be applied on photooxidation of AsIII and adsorption of AsV. Under optimal conditions, maximum adsorption capacities (Qmax) values of 254 and 168 mg g- 1 were reached for AsIII adsorption by MOF and membrane, respectively. Notably, for AsV adsorption, Qmax values of 268 and 335 mg g- 1 were reached for powdered and immobilized MOF, respectively. Moreover, the membrane keeps most of its activity for AsV adsorption when employed in surface and groundwater matrixes. Further, the efficiently of UiO-66-NH2 to photo-oxidize AsIII to AsV, subsequently adsorbing the arsenate oxyanions, is improved by a factor of five when is integrated into the polymer. A detailed multi-step mechanism for the arsenic transformation and adsorption in CHIPEC@UiO-66-NH2 has been proposed on the basis of the anionic exchange at Zr hexa-nuclear clusters and amino groups in the MOF. Overall, MOFbiopolymeric composite has been proved as a straightforward, efficient, low-cost, and environmentally friendly solution for detoxifying arsenic in surface and underground water.

Abstract Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) is a highly versatile polymer used for water remediation due to its chemical robustness and processability. By incorporating metal‐organic frameworks (MOFs) into PVDF‐HFP membranes, the material can gain metal‐adsorption properties. It is well known that the effectiveness of these composites removing heavy metals depends on the MOF's chemical encoding and the extent of encapsulation within the polymer. In this study, it is examined how the micro to nanoscale structure of PVDF‐HFP@MOF membranes influences their adsorption performance for CrVI. To this end, the micro‐ and nanostructure of PVDF‐HFP@MOF membranes are thoroughly studied by a set of complementary techniques. In particular, small‐angle X‐ray and neutron scattering allow to precisely describe the nanostructure of the polymer‐MOF complex systems, while scanning microscopy and mercury porosimetry give a clear insight into the macro and mesoporosity of the system. By correlating nanoscale structural features with the adsorption capacity of the MOF nanoparticles, different degrees of full encapsulation‐based on the PVDF‐HFP processing and structuration from the macro to nanometer scale are observed. Additionally, the in situ functionalization of MOF nanoparticles with cysteine is investigated to enhance their adsorption toward HgII. This functionalization enhanced the adsorption capacity of the MOFs from 8 to 30 mg·g−1.

Natural or industrial hexavalent chromium water pollution continues to be a worldwide unresolved threat. Today, there is intense research on new active and cost-effective sorbents for Cr(VI), but most still exhibit a critical limitation: their powdered nature makes their recovery from water cost and energy consuming. In this work, Al(OH)3, MIL-88-B(Fe), and UiO-66-NH2 Cr(VI) sorbents were immobilized into a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymeric substrate to develop an easily reactivable and reusable water filtering technology. The immobilization of the sorbents into the PVDF-HFP porous matrix modified the macro and meso-porous structure of the polymeric matrix, tuning in parallel its wettability. Although a partial blocking of the Cr(VI) adsorptive capacity was observed for of Al(OH)3 and MIL-88-B(Fe) when immobilized into composite membranes, PVDF-HFP/UiO-66-NH2 filter (i) exceeded the full capacity of the non-immobilized sorbent to trap Cr(VI), (ii) could be reactivated and reusable, and (iii) it was fully functional when applied in real water effluents.

Abstract Nanocomposite membranes (NCMs) of poly(vinylidene fluoride‐hexafluoropropylene), PVDF‐HFP, with different yttrium carbonate and magnetite loadings, are prepared, and their dual adsorption capacity over neutral arsenite and anionic arsenate species is evaluated. The nanoparticles (NPs) and the corresponding NCMs are fully characterized in morphology, microstructure, thermal, and surface properties. The nanocomposite membranes present a micrometric porous structure with a homogeneous distribution of the active nanoparticles. Chemical, thermal, and water‐contact angle characteristics of the NCMs point out that they maintain the chemical and thermal stability of the polymer while improving the wettability. Arsenic removal depends on NP loading and pH of the media. For instance, efficiencies close to 100% are achieved for arsenate species under acidic conditions, while adsorption capacity over arsenite is also incremented above 80%. Fe3O4/PVDF‐HFP nanocomposite shows a dual affinity for the adsorption of As(III) and As(V) species, with the maximum adsorption capacities of 92.82 and 137.08 mg g−1, respectively. In addition, both NCMs are easily activated and reused without significant efficiency loss. Consequently, the nanocomposite membranes represent low‐cost, reusable, and efficient water remediation systems suitable for the long‐term removal of As(III) and As(V) under conditions mimicking real polluted surface and groundwater.

The use of metal-organic frameworks in the separator membrane of lithium-ion batteries is an interesting subject of study for the next generation of energy storage devices. In this work, different poly(vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP) / metal-organic framework (MOF) based separators were prepared using three distinct MOFs, and the properties of these membranes were studied. The selected MOFs MOF-808, UiO-66NH2 and MIL-125 are characterized by sharing a common building block (cluster or linker) and possessing relatively similar surface areas and topologies. It is observed that there are significant variations in the porous structure of the separator membrane upon the introduction of the different MOFs. The use of MOFs reduces the resistivity of the assembled battery half-cells, leading to excellent battery performance, with high discharge capacity (145 mAh.g(-1) at C/8) and prolonged lifecycle, outperforming e conventional neat polymer separators due to the structure's stabilization effect of the MOF. Among the selected MOFs, the best results are achieved with UiO-66-NH2 based on its improved charge/discharge values due to the low resistivity value of the half-cell. The post-morten analysis shows that the MOF structure collapses during battery cycling, but that this fact does not significantly affect battery performance, as the produced nanofillers keep their role of minimizing battery capacity fading. Thus, it is demonstrated that adding MOFs to a polymeric separator structure is beneficial and suitable for high-performance battery applications.

Hexavalent chromium (Cr(VI)) is a highly mobile cancerogenic and teratogenic heavy metal ion. Among the varied technologies applied today to address chromium water pollution, photocatalysis offers a rapid reduction of Cr(VI) to the less toxic Cr(III). In contrast to classic photocatalysts, Metal-Organic frameworks (MOFs) are porous semiconductors that can couple the Cr(VI) to Cr(III) photoreduction to the chromium species immobilization. In this minireview, we wish to discuss and analyze the state-of-the-art of MOFs for Cr(VI) detoxification and contextualizing it to the most recent advances and strategies of MOFs for photocatalysis purposes. The minireview has been structured in three sections: (i) a detailed discussion of the specific experimental techniques employed to characterize MOF photocatalysts, (ii) a description and identification of the key characteristics of MOFs for Cr(VI) photoreduction, and (iii) an outlook and perspective section in order to identify future trends.

The fast‐increasing interest in multivariate metal–organic frameworks (MTV‐MOFs) has burgeoned due to the possibility to create synergetic functions and achieve performance significantly better than their simple sum. In this work, the opportunities and the effects of multivariate functionalization of UiO‐66 on diverse properties important for photocatalytic water remediation: hydrolytic stability, bandgap energy, photoconduction, Cr VI and Cr III adsorption capacity and kinetics, and Cr VI to Cr III photoreduction efficiency, are explored. By developing a (Zr)UiO‐66‐NH 2 ‐(OH) 2 ‐NO 2 multivariate material based on the combination of 2‐aminoterephthalate, 2,5‐dihydroxyterephthalate, and 2‐nitroterephthalate organic linkers in the same framework, a dual sorbent/photocatalyst is developed for water remediation with excellent properties: 1) enhanced adsorption efficiency of Cr VI and Cr III ions, 2) improved photocatalytic conversion of Cr VI to Cr III , and 3) with suitable chemical stability under acidic conditions for catalytic applications. This work represents a milestone for an emerging class of reticular materials that can synergistically use the properties of individual functionalities to solve complex problems beyond just the water remediation application discussed in this paper.

Metal chelators and porous sorbents are two of the forefront technologies applied for the recovery and separation of hazardous and/or valuable metal ions from aqueous solutions (i.e., polluted water sources, metal-rich mining wastewaters, acid leachates, and so forth). The transfer of the metal coordination functions of metal chelators to chemically stable host materials had only limited success so far. Here, we report the installation of natural acids (i.e., malic acid, mercaptosuccinic acid, succinic acid, fumaric acid, and citric acid) and amino acids (i.e., histidine, cysteine, and asparagine) within a porous zirconium-based trimesate metal-organic framework (MOF), namely, MOF-808. Applying this strategy, we were able to produce a pore environment spatially decorated with multiple functional groups usually found in commercial chelator molecules. The chemical stability of the amino acid molecules installed by the solvent-assisted ligand exchange has been studied to delimitate the applicability window of these materials. The adsorption affinity of MOF-808@(amino)acids in static and column-bed configurations can be finetuned as a function of the amino acid residues installed in the framework. MOF-808(amino)acid columns can be applied efficiently both for water remediation of heavy metals and for the separation of metal ions with different acidities. For instance, the initial trends for the dispersion of rare-earth elements have been identified. Electron paramagnetic resonance and inelastic neutron scattering spectroscopy reveal that MOF-808@(amino)acids stabilize metal centers as isolated and clustered species in a coordination fashion that involves both the amine and thiol functionals and that affects the vibrational freedom of some of the chemical groups of the amino acid molecules. The metal-ion stabilization within amino acid-decorated MOFs opens the avenue for application for pseudo biocatalysis purposes in the near future.

The presence of hexavalent chromium water pollution is a growing global concern. Among the currently applied technologies to remove CrVI, its adsorption and photocatalytic reduction to CrIII less mobile and toxic forms are the most appealing because of their simplicity, reusability, and low energy consumption. However, little attention has been paid to bifunctional catalysts, that is, materials that can reduce CrVI to CrIII and retain both hexavalent and trivalent chromium species at the same time. In this work, the dual CrVI adsorption–reduction capacity of two iconic photoactive water-stable zirconium and titanium-based metal–organic frameworks (MOFs) has been investigated: UiO-66-NH2 and MIL-125. The bifunctionality of photoactive MOFs depends on different parameters, such as the particle size in MIL-125 or organic linker functionalization/defective positions in UiO-66 type sorbents. For instance, the presence of organic linker defects in UiO-66 has shown to be detrimental for the chromium photoreduction but beneficial for the retention of the CrIII phototransformed species. Both compounds are able to retain from 90 to 98% of the initial chromium present at acidic solutions as well as immobilize the reduced CrIII species, demonstrating the suitability of the materials for CrVI environmental remediation. In addition, it has been demonstrated that adsorption can be carried out also in a continuous flux mode through a diluted photoactive MOF/sand chromatographic column. The obtained results open the perspective to assess the bifunctional sorption and photoreduction ability of a plethora of MOF materials that have been applied for chromium capture and photoreduction purposes. In parallel, this work opens the perspective to develop specific chemical encoding strategies within MOFs to transfer this bifunctionality to other related water remediation applications.

Lightweight Metal Organic Framework adsorbents are chemically versatile and highly porous materials that have been widely tuned to enhance their affinity and capacity to capture metal ions with different chemical natures from aqueous environments. In this chapter, the key chemical features within the MOF chemistry to recover effectively cationic and anionic species from different environments have been described, reviewing in detail their performance to capture heavy metals, precious metal ions, radioactive elements, technologically relevant rare earth elements, chromium, arsenic, and other oxyanions. Depending on the application-specific cases, their performance from single-element dilute solution to highly stringent conditions such as multi-element, radioactive, acidic, aqueous wastes will be described in terms of adsorption capacity, affinity, and reusability. Special attention will be paid to describe the adsorption mechanisms that have been doubtlessly solved, as well as to the multimethodological techniques applied to unravel them.

Composites based on chitin (CH) biopolymer and metal-organic framework (MOF) microporous nanoparticles have been developed as broad-scope pollutant absorbent. Detailed characterization of the CH/MOF composites revealed that the MOF nanoparticles interacted through electrostatic forces with the CH matrix, inducing compartmentalization of the CH macropores that led to an overall surface area increase in the composites. This created a micro-, meso-, and macroporous structure that efficiently retained pollutants with a broad spectrum of different chemical natures, charges, and sizes. The unique prospect of this approach is the combination of the chemical diversity of MOFs with the simple processability and biocompatibility of CH that opens application fields beyond water remediation.

Poly(vinylidene fluoride) (PVDF) and MOF-808-based separators for lithium-ion batteries (LIBs) have been prepared and fully characterized in terms of morphological and thermal properties, electrolyte uptake, and retention, and surface hydrophilic characteristics. The effect of PVDF/MOF-808 separators on the electrochemical performance of LIBs has been evaluated. The PVDF/MOF-808 membranes exhibit a well-defined porous structure with a uniform distribution of interconnected macro- to mesopores. The inclusion of the Zr-based MOF nanoparticles increases the porosity and surface area of the separator, enhancing the electrolyte uptake and the ionic conductivity. Finally, the presence of MOF-808 fillers improves the liquid electrolyte retention, which prevents the capacity fading at high C-rates cycling. Indeed, charge-discharge tests performed in Li/C-LiFePO4 half-cells reveal a discharge capacity of 68 mAh..g(-1) at 2C-rate for PVDF/MOF-808 membranes, in comparison with the 0 mAh.g(-1) obtained for pure PVDF. The PVDF/10 wt % MOF-808 sample shows a long-term stable cycling behavior with a Coulombic efficiency close to 100%. Thus, it is shown that the composite membranes represent an improvement with respect to conventional separators for lithium ion battery applications, since they coupled the polymer meso- and macroporous structure with the wellordered microporous system of the MOFs, which improve significantly the electrolyte affinity.

Bacterial contamination is a critical problem in medical implants, which are preferential sites for bacterial adhesion, leading to infections which can compromise health and immune system of patients. Commercial titanium alloys are the most commonly used materials for permanent implants in contact with bone, and the prevention of infections on their surface is therefore a crucial challenge for orthopaedic and dental surgeons. Thus, the aim of this work is to develop polysaccharide antibacterial coatings onto modified titanium surfaces with different surface topography, in order to act as reservoirs of antibacterial agents. For this, hyaluronic acid/chitosan polyelectrolyte multilayers were successfully developed after acid hydrolysis of Ti-6Al -4 V alloys. Surface modification could be monitorized by XPS spectroscopy, fluorescence confocal microscopy and contact angle measurements. Furthermore, the effect of surface micropatterning on the stability, hydrophilicity, capability to the loading and release of triclosan and the antibacterial properties of prepared multilayers against Staphylococcus aureus were also analysed.

There is a great demand for new materials in the field of biomedicine to be used as implants, however they cause rejection problems due to their lack of biocompatibility. In this work two substrates (inorganic and polymeric) will be surface modified using the layer by layer strategy (LbL), in order to construct hyaluronic and chitosan multilayers. It has been proven that the layers were successfully built by fluorescent confocal microscopy by means of the increase of fluorescence along layers deposition after fluorescent labelling of chitosan. Thanks to this, it has been possible to increase the hydrophilicity of the surfaces enhancing antibacterial properties and getting more biocompatible materials in a simple and inexpensive way.

Biomedikuntza arloan inplante moduan erabiltzeko material berrien eskaera handia dago, baina errefus arazoak sortzen dituzte biobateragarritasun kontuak direla eta. Lan honetan azalduko dugu nola eraldatu dugun bi substratu motaren gainazala. Bat ezorganikoa izango da eta bestea polimerikoa. Geruzaz geruzako («layer by layer») estrategiaz baliatuta, azido hialuroniko eta kitosanozko multigeruzak sortuko dira. Kitosanoa fluoreszenteki markatu eta mikroskopio konfokalean fluoreszentzia- hazkundea behatu ondoren, ondorioztatu da geruzak modu arrakastatsu batean sortu direla. Honi esker, materialaren hidrofilitatea areagotzea lortu da, eta horrela, bakterioen aurkako gainazala lortzeaz gainera materialaren biobateragarritasuna handituko da modu merke eta sinple batean.

espanolEl desarrollo de nuevos materiales requiere a menudo del desarrollo de novedosos recubrimientos. Una estrategia prometedora para ello es el autoensamblado de capas que permitan anadir nuevas funcionalidades, asi como, la implementacion de la estructura y el orden nanometrico sin aumentar en demasia su coste. Asi, la formacion de recubrimientos por medido de tecnicas de deposicion capa a capa es una tecnica sencilla, versatil y de bajo coste que se utiliza para la preparacion de peliculas delgadas mediante la adsorcion alternante de polimeros complementarios como pueden ser aquellos cargados positiva y negativamente, o con grupos donantes y receptores de enlaces de hidrogeno. Las peliculas delgadas de multicapas pueden utilizarse en diversas aplicaciones, algunas de las mas relevantes reflejadas en esta revision, como pueden ser la fabricacion de membranas, en aplicaciones biomedicas o en la industrial de la alimentacion EnglishThe development of new materials often requires obtaining novel coatings. A promising strategy is the self-assembly of layers that allow adding new functionalities, as well as, the implementation of the structure and the nanometric order without increasing its cost too much. Thus, the formation of coatings by layer-by-layer deposition techniques is a simple, versatile and low cost technique that is used for the formation of thin films by the alternating adsorption of complementary polymers such as those charged positively and negatively, or with hydrogen bond donor and receptor groups. Thin multilayer films can be used in various applications, some of the most relevant being summarized in this review, such as the manufacture of membranes, biomedical applications or the industrial food industry applications