6.1 Oberflächen- und Dünnschichtanalyse
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Open Metal Sites Govern Hydration Kinetics and Molecular Fluctuations in Metal−Organic Frameworks
(2026)
Water under nanoscale confinement exhibits structural and dynamical states distinct from bulk behavior, yet the role of pore chemistry in governing these states remains insufficiently understood. Herein, the hydration kinetics and molecular-scale fluctuations of water confined within a comprehensive series of MOF-74 metal-organic frameworks incorporating Mg, Ni, Co, and mixed-metal compositions were investigated and compared with those observed in mesoporous MCM-41 silica. In situ impedance spectroscopy resolves a pronounced multistep hydration mechanism in MOF-74, initiated by rapid coordinative binding at open metal sites, followed by cluster formation and final capillary condensation. In contrast to MCM-41 silica, where capillary condensation dominates, the presence of coordinatively unsaturated metal centers fundamentally alters adsorption pathways. Mixedmetal MOF-74 exhibits accelerated and temporally broadened hydration, reflecting heterogeneous distributions of adsorption energies. Broadband dielectric spectroscopy reveals a distinct water-specific relaxation process (w-relaxation) attributed to fluctuations of water clusters interacting with metal nodes. Relaxation rates follow Arrhenius behavior with activation energies increasing in the order Mg < Ni < Co and further enhanced in mixed-metal systems. Remarkably, water confined within MOF-74 remains liquid-like down to 133 K without crystallization, whereas crystallization is observed in MCM-41 silica. All activation data of the MOF-74 systems obey a common Meyer−Neldel compensation relation, indicating cooperative molecular dynamics and suggesting a hindered glass-transition−like process of confined water clusters. These findings demonstrate that open metal sites and metal composition enable programmable control over hydration kinetics and collective water dynamics in microporous frameworks. MOF-74 thus provides a tunable model platform for engineering water-driven transport, catalysis, and energy-relevant processes atthe nanoscale.
A sustainable mechanochemical process for the generation of sodium aluminium fluorides by conversion of polyvinylidene fluoride (PVDF) waste on using ball milling in the presence of a Lewis acid was developed. The generated fluorides can be key materials for the aluminium production process. The Lewis acid AlCl3 initiates dehydrofluorination steps at PVDF, releasing HF for further fluorination of both NaCl and AlCl3 to yield chiolite under ball milling conditions. Further calcination of chiolite generates cryolite with an overall yield of 62% with respect to AlCl3. The procedure avoids the use of solvents and minimises energy consumption. The identity and phase purity of the products was confirmed by XRD, NMR, IR, and Raman analyses. It was also demonstrated that powdered PVDF, real-life PVDF membrane waste orPVDFextracted from Li-ion batteries can be upcycled into industrially relevant fluoride materials. The presented method offers a sustainable approach for resource recovery and environmental remediation.
Die für die Sicherheit von Mensch und Umwelt sowie für die Messtechnik zuständigen deutschen Bundesbehörden – das Umweltbundesamt, die Bundesanstalt für Arbeitsschutz und Arbeitsmedizin (BAuA), das Bundesinstitut für Risikobewertung (BfR), die Bundesanstalt für Materialforschung und -prüfung (BAM) und die Physikalisch-Technische Bundesanstalt (PTB) – begleiten die rasante Innovation von neuartigen Materialien mit einer langfristigen Forschungsstrategie. Die vorgestellte Strategie zeigt die notwendige Sicherheitsforschung auf, die auf der einen Seite Regulierungsbehörden in die Lage versetzt, neuartige Materialien angemessen bewerten zu können, und auf der anderen Seite auch das „Safe and Sustainable by Design“ für Innovatoren unterstützt.
The German federal authorities responsible for human and environmental safety, and metrology – the German Environment Agency (UBA), the Federal Institute for Occupational Safety and Health (BAuA), the German Federal Institute for Risk Assessment (BfR), the Federal Institute for Materials Research and Testing (BAM), and the National Metrology Institute (Physikalisch-Technische Bundesanstalt, PTB) - are accompanying the rapid pace of innovation of advanced materials with a long term research strategy focusing on safety research needs from a regulatory perspective. The strategy builds on former joint research strategies on nanomaterials and advanced materials and highlights current research priorities to enable regulatory preparedness for material innovations and better connect safety research with innovation research.
The ACCORDs project (Green Deal inspired correlative imaging-based characterization for safety profiling of 2D materials) is developing an integrated Knowledge Infrastructure to support harmonised characterization workflows for graphene-family materials and other advanced materials. The platform connects imaging data, physico-chemical characterization, biological testing, and risk-related information within a structured and FAIR-compliant environment.
The ACCORDs Knowledge Infrastructure brings together datasets, microscopy images, protocols, and analysis workflows, enabling reproducible characterization approaches and facilitating collaboration across disciplines. The system supports the integration of physico-chemical and biological endpoints, links experimental results to materials and protocols, and enables advanced data analysis, AI/ML-supported workflows, and decision support for safety profiling.
This online event aims to introduce the ACCORDs project and demonstrate the capabilities of the Knowledge Infrastructure, including the image atlas, protocol integration, multi-modal characterization approaches, and practical use cases involving graphene-family materials, with potential applicability to other advanced materials.
The session will combine short expert contributions from project partners with a live demonstration of the ACCORDs Knowledge Infrastructure.
Accurate determination of particle number concentration is essential in the industry as well the healthcare sector. Widely applied methods for the measurement of particle number concentration, such as MADLS, SAXS, spICP-MS, rely on material specific input parameters, modelling assumptions, or calibration strategies, which contribute to measurement uncertainty, making absolute quantification challenging and limiting direct metrological traceability. In the framework of the European project ConcenSus (https://concensusproject.org/home), a dedicated approach is being studied to determine (nano)particle number concentration using imaging methods. SEM, TEM and other imaging methods are well established for characterising the sizes and shapes of advanced materials with ISO standards in place. (ISO 19749:2021, ISO 21363:2020) However, no corresponding standard operation procedures exist for (nano)particle number concentration determination using imaging methods. This work presents a proof-of-principle study for determining the particle number concentration using SEM by employing a dedicated sample preparation method. First, relatively simpler materials such as Ag and Pd nanoparticles have been tested, with future project work increasing particle complexity to include other material types, for example, liposomes, QDs, mesoporous SiO2, etc. The performance of our approach has been assessed by comparison with concentrations measured with MADLS. The results obtained with both methods are in the same order of magnitude (10E11 particles/mL), which demonstrate the strong potential of SEM combined with dedicated sample preparation as a powerful method for the number metrology of (nano)particles independent of material-type and theoretical assumptions, focusing mainly on direct particle counting. Further optimisation of the sample preparation will enable an automated workflow for the measurement of particle number concentration by imaging.
Accurate analysis of microplastics is based on validated methods and the use of standardised protocols. Therefore, reference materials are essential to determine recovery rates and optimise the existing workflows. Reference materials are well characterised, as well as homogenous and stable in at least one property of interest (Emteborg, 2024). They are intended for a defined use and should mimic the reality in terms of selected particle properties and concentrations. Especially for micro- and nanoplastics, aged surfaces and irregular shapes should be covered. The Quality-by-Design approach helps to select the users need and defines a target product profile with mandatory and desired particle properties (Altmann, 2025). After defining the target specifications, the particle production must be controlled and the particles need to be well characterised. An optimisation process helps to guarantee a consistently high-quality product that complies with the chosen specifications, even over repeated batches. Finally, the materials should be tested for their performance in the intended application and validated for homogeneity and stability. We will address different top-down production processes with their limits and challenges, especially when varying polymer type, shape and size ranges. The required concentration may also need to vary between mg and µg depending on the intended use. For example, when considering the Urban Wastewater Treatment Directive and the monitoring of microplastics in the influent and effluent of the wastewater stream as well as sludge, dfferent needs for various plastics and concentrations are required. The effluent will have less microplastics compared to the influent, while the sludge will likely vary in the polymer types present. Thus, polymer types for particle production should focus on thermoplastics such as polyethylene, polypropylene, polystyrene and polyethylene terephthalate, which are relevant in these scenarios.
Reliable quantification of the chemical composition of graphene-related 2D materials (GR2M) as powders and liquid suspensions is a challenging task. Analytical methods such as X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) are recommended by standardization bodies. The specific parameters to be measured are also defined, e.g., the oxygen-to-carbon (O/C) atomic ratio, the trace metal impurities, or the functional groups. In this contribution, for the first time, results of a systematic study on the capability of energy-dispersive X-ray spectroscopy (EDS) at a scanning electron microscope (SEM) to reliably quantify the O/C ratio and impurities remained from the synthesis of selected GR2M are reported. The robustness of SEM/EDS analysis is verified for various measurement conditions (different excitations and EDS detectors) and the validity of the results is tested by comparison to the established XPS analysis. Moreover, an ionic liquid is used as a reference material for the quantification of the light elements such as C, N, O and F. The study clearly demonstrates the reliability of the fast and widely available SEM/EDS as a standard method for the quantification of the elemental composition of GR2M and generally of light materials.
Proper physicochemical characterization of advanced materials and complex industrial composites remains a significant challenge, particularly for nanomaterials, whose nanoscale dimensions and mostly complex chemistry challenge the analysis. In this work, we employed a correlative analytical approach that integrates atomic force microscopy (AFM), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS), time-of-flight secondary ion mass spectrometry (ToF- SIMS), Auger electron spectroscopy (AES), and Raman spectroscopy. This combination enables detailed chemical and structural characterization with sub-micrometer spatial resolution. Three commercial graphene-based materials of varying complexity were selected and investigated to test the analytical performance of this approach. Furthermore, one of the commercial graphene oxide samples was chemically functionalized via amination and fluorination. This allowed us to assess how surface modifications influence both the material properties and the limits of the applied analytical techniques.
High spatial frequency laser‐induced periodic surface structures (HSFL) exhibiting sub‐100 nm spatial periods – far below the optical diffraction limit – can be easily manufactured on titanium and its alloys by laser‐based processes. The regularity of these HSFL – expressed in the length and local orientation of the ridges – is not only influenced by the parameters chosen for the laser scanning process but also by the microscale morphology of the titanium substrates. We processed HSFL on titanium materials with varying microscale morphology (bulk, film) by irradiation with near‐infrared ps‐laser pulses (1030 nm wavelength, ≈1 ps pulse duration) under different laser scanning conditions with the aim to increase the order of the nanoscale surface structures. For quantification of the regularity of the HSFL, a detailed analysis of scanning electron microscopic images is performed with our free ReguΛarity software to yield large area morphological and topographical surface characterization. Analyses of the regularity of the HSFL are performed with respect to the influences of sample- or laser-related parameters and the ablation thresholds.