Polyoxometalates on Functional Substrates: Concepts, Synergies, and Future Perspectives

Polyoxometalates (POMs) are molecular metal oxide clusters that feature a broad range of structures and functionalities, making them one of the most versatile classes of inorganic molecular materials. They have attracted widespread attention in homogeneous catalysis. Due to the challenges associated with their aggregation, precipitation, and degradation under operational conditions and to extend their scope of applications, various strategies of depositing POMs on heterogeneous substrates have been developed. Recent ground-breaking developments in the materials chemistry of supported POM composites are summarized and links between molecular-level understanding of POM-support interactions and macroscopic effects including new or optimized reactivities, improved stability, and novel function are established. Current limitations and future challenges in studying these complex composite materials are highlighted, and cutting-edge experimental and theoretical methods that will lead to an improved understanding of synergisms between POM and support material from the molecular through to the nano- and micrometer level are discussed. Future development in this fast-moving field is explored and emerging fields of research in POM heterogenization are identified

Evaluating the durability and performance of polyoxometalate-ionic liquid coatings on calcareous stones: Preventing biocolonisation in outdoor environments

Rock-based materials exposed to outdoor environments are naturally colonised by an array of microorganisms, which can cause dissolution and fracturing of the natural stone. Biocolonisation of monuments and architectures of important cultural heritage therefore represents an expensive and recurring problem for local authorities and private owners alike. In this area, preventive strategies to mitigate biocolonisation are generally preferred to curative approaches, such as mechanical cleaning by brush or high-pressure cleaning, to remove pre-existing patina. The aim of this work was to study the interaction between biocidal polyoxometalate-ionic liquid (POM-IL) coatings and calcareous stones and evaluate the capacity of these coatings to prevent biocolonisation through a series of accelerated ageing studies in climate chambers, carried out in parallel with a two-year period of outdoor exposure in north-eastern France. Our experiments show that POM-IL coatings did not affect water vapour transfer nor significantly alter the total porosity of the calcareous stones. Simulated weathering studies replicating harsh (hot and wet) climatic weather conditions demonstrated that the colour variation of POM-IL-coated stones did not vary significantly with respect to the natural uncoated stones. Accelerated biocolonisation studies performed on the weathered POM-IL-coated stones proved that the coatings were still capable of preventing colonisation by an algal biofilm. However, a combination of colour measurements, chlorophyll fluorescence data, and scanning electron microscopy imaging of stones aged outdoors in northern France for two years showed that coated and uncoated stone samples showed signs of colonisation by fungal mycelium and phototrophs. Altogether, our results demonstrate that POM-ILs are suitable as preventative biocidal coatings for calcareous stones, but the correct concentrations must be chosen to achieve a balance between porosity of the stone, the resulting colour variation and the desired duration of the biocidal effect over longer periods of time, particularly in outdoor environments

Alkoxy-functionalized ionic liquid electrolytes: Understanding ionic coordination of calcium ion speciation for the rational design of calcium electrolytes

There is growing interest in the rational design of electrolytes for multivalent-ion batteries by tuning the molecular-level interactions of solvate species present in the electrolytes. Herein, we report our effort to control Ca-ion speciation in ionic liquid (IL) based electrolytes through the design of alkoxy-functionalized cations. Quantitative analysis reveals that the alkoxy-functionalized ammonium cation (N$_{07}$$^{+}$), bearing seven ether oxygen atoms, can effectively displace the bis(trifluoromethanesulfonyl)imide anion (TFSI$^{-}$) from the Ca$^{2+}$ ion coordination sphere, facilitating the reversible Ca deposition/stripping process. More importantly, post-analysis of Ca deposits surface chemistry and density functional theory calculations of Ca-ion speciation indicate the formation of an organic-rich, but inorganic-poor solid electrolyte interphase layer, which enables Ca$^{+2}$ ion diffusion rather than passivating the Ca metal electrode. Finally, as a proof-of-concept, a prototype Ca/V$_{2}$O$_{5}$ cell using the optimized IL-based electrolyte ([Ca(BH$_{4}$)$_{2}$]$_{0.05}$ [N$_{07}$TFSI]$_{0.95}$) is demonstrated for the first time, exhibiting a remarkable initial discharge capacity of 332 mA h g$^{-1}$ and reversible capacity of 244 mA h g$^{-1}$

Novel Polyoxometalate- Ionic Liquid with Antibacterial and Antifungal Properties. Feasibility of Its Implementation As a Multifunctional Thin Coating

The synthesis of hybrid materials, combining the properties of organic and inorganic components, results in composites with unique physical and chemical features. Polyoxometalates (POMs), i.e. inorganic anionic molecular metal oxides, are considered as promising future metallodrugs due to their antiviral, antitumoral and antibacterial activities. The combination of bulky organic cations with POMs results in composite ionic liquids (IL; melting point below 100°C) which combine the unique properties of both components. Pioneering studies have used composites of alkylammonium cations and POM anions for multifunctional water purification to remove toxic heavy materials, organic aromatics and microbes and for the inhibition of bio-corrosion on metal and stone surfaces due to coating formation.Fil: Enderle, Ana Gabriela. Universidad Nacional del Litoral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Streb, C.. Universitat Ulm; AlemaniaFil: Bollini, Mariela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Culzoni, Maria Julia. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Química. Cátedra de Química Analítica; ArgentinaFil: Mitchell, S. G.. Universidad de Zaragoza; EspañaFil: Franco Castillo, I.. Universidad de Zaragoza; España2019 AIChE Annual MeetingOrlandoEstados UnidosAmerican Institute of Chemical Engineer

Redox-inactive ions control the redox-activity of molecular vanadium oxides

Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca$^{2+}$ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca$^{2+}$-functionalized dodecavanadate [Ca$_{2}$V$_{12}$O$_{32}$Cl(DMF) $_{3}$]$^{2-}$ (={Ca$_{2}$V$_{12}$}) was thus compared with that of the precursor compound (H$_{2}$NMe$_{2}$)$_{2}$ [V$_{12}$O$_{32}$Cl] $^{3-}$ (={V$_{12}$}). {Ca$_{2}$V$_{12}$} can store up to five electrons per cluster, while {V12} only shows one reversible redox transition. In initial studies, we demonstrated that {Ca$_{2}$V$_{12}$} can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates

Catching-up and falling behind knowledge spillover from American to German machine tool makers

In our days, German machine tool makers accuse their Chinese competitors of violating patent rights and illegally imitating German technology. A century ago, however, German machine tool makers used exactly the same methods to imitate American technology. To understand the dynamics of this catching-up process we use patent statistics to analyze firms? activities between 1877 and 1932. We show that German machine tool makers successfully deployed imitating and counterfeiting activities in the late 19th century and the 1920s to catchup to their American competitors. The German administration supported this strategy by stipulating a patent law that discriminated against foreign patent holders and probably also by delaying the granting of patents to foreign applicants. Parallel to the growing international competitiveness of German firms, however, the willingness to guarantee intellectual property rights of foreigners was also increasing because German firms had now to fear retaliatory measures in their own export markets when violating foreign property rights within Germany

New protective coatings against lampenflora growing in the Pommery Champagne cellar

Phototrophic microorganisms such as cyanobacteria and microalgae can proliferate readily in underground heritage sites where the introduction of artificial illumination equipment has significantly altered previously stable environmental conditions. The extended lampenflora biofilm growth on the bas-reliefs carved in the underground Pommery Champagne cellar in Reims (France) represents a recurring biocolonisation problem which requires periodic cleaning. The aim of this work was to limit the growth of lampenflora on chalk substrates using preventative biocidal treatments based on polyoxometalate ionic liquids (POM-ILs). Biocidal assays carried out in laboratory showed how two different colourless POM-IL coatings were more effective than commercial Preventol RI80 against two algal strains isolated from the Pommery bas reliefs, Pseudostichococcus monallantoides and Chromochloris zofingiensis. However, only one POM-IL variant was capable of sustained prevention of biofilm growth when applied to wet chalk, which replicates the more drastic natural environmental conditions of the cellar and can limit the performance of the biocidal coatings. Crucially, coating concentration studies demonstrate how POM-IL-coated slabs from previous experiments retain their biocidal activity and can prevent subsequent recolonisation following the re-inoculation of coated slabs with algae and cyanobacteria. Consequently, POM-ILs represent excellent candidates to eliminate lampenflora growth on the chalk bas-reliefs in the unique subterranean environment of the Pommery Champagne cellar. © 2022 The Author

Multifunctional Polyoxometalate Platforms for Supramolecular Light-Driven Hydrogen Evolution

Multifunctional supramolecular systems are a central research topic in light-driven solar energy conversion. Here, we report a polyoxometalate (POM)-based supramolecular dyad, where two platinum-complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light-driven hydrogen evolution. Combined theory and experiment demonstrate the multifunctionality of the POM, which acts as photosensitizer/catalyst-binding-site[1] and facilitates light-induced charge-transfer and catalytic turnover. Chemical modification of the Pt-catalyst site leads to increased hydrogen evolution reactivity. Mechanistic studies shed light on the role of the individual components and provide a molecular understanding of the interactions which govern stability and reactivity. The system could serve as a blueprint for multifunctional polyoxometalates in energy conversion and storage