Archismita Misra’s research while affiliated with Federal Institute For Materials Research and Testing and other places

Corrosion of metals and other materials in marine environments poses significant economic, operational, safety, and environmental challenges across the oil and gas industry, the renewable energy sector, and maritime infrastructure....

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.

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.

Core-shell materials are promising functional materials for fundamental research and industrial application, as their properties can be adapted for specific applications. In particular, particles featuring iron or iron oxide as core material are relevant since they combine magnetic and catalytic properties. The addition of an SiO2 shell around the core particles introduces additional design aspects, such as a pore structure and surface functionalization. Herein, we describe the synthesis and application of iron-based core-shell nanoparticles for two different fields of research that is heterogeneous catalysis and water purification. The iron-based core shell materials were characterized by transmission electron microscopy, as well as N2-physisorption, X-ray diffraction, and vibrating-sample magnetometer measurements in order to correlate their properties with the performance in the target applications. Investigations of these materials in CO2 hydrogenation and water purification show their versatility and applicability in different fields of research and application, after suitable individual functionalization of the core-shell precursor. For design and application of magnetically separable particles, the SiO2 shell is surface-functionalized with an ionic liquid in order to bind water pollutants selectively. The core requires no functionalization, as it provides suitable magnetic properties in the as-made state. For catalytic application in synthesis gas reactions, the SiO2-stabilized core nanoparticles are reductively functionalized to provide the catalytically active metallic iron sites. Therefore, Fe@SiO2 core-shell nanostructures are shown to provide platform materials for various fields of application, after a specific functionalization.

Filtration is an established water‐purification technology. However, due to low flow rates, the filtration of large volumes of water is often not practical. Herein, we report an alternative purification approach in which a magnetic nanoparticle composite is used to remove organic, inorganic, microbial, and microplastics pollutants from water. The composite is based on a polyoxometalate ionic liquid (POM‐IL) adsorbed onto magnetic microporous core–shell Fe2O3/SiO2 particles, giving a magnetic POM‐supported ionic liquid phase (magPOM‐SILP). Efficient, often quantitative removal of several typical surface water pollutants is reported together with facile removal of the particles using a permanent magnet. Tuning of the composite components could lead to new materials for centralized and decentralized water purification systems.

Polyoxometalates (POMs) are molecular metal‐oxide anions applied in energy conversion and storage, manipulation of biomolecules, catalysis, as well as materials design and assembly. Although often overlooked, the interplay of intrinsically anionic POMs with organic and inorganic cations is crucial to control POM self‐assembly, stabilization, solubility, and function. Beyond simple alkali metals and ammonium, chemically diverse cations including dendrimers, polyvalent metals, metal complexes, amphiphiles, and alkaloids allow tailoring properties for known applications, and those yet to be discovered. This review provides an overview of fundamental POM–cation interactions in solution, the resulting solid‐state compounds, and behavior and properties that emerge from these POM–cation interactions. We will explore how application‐inspired research has exploited cation‐controlled design to discover new POM materials, which in turn has led to the quest for fundamental understanding of POM–cation interactions.