TY - CONF A1 - Linberg, Kevin T1 - Polymorphism in molecular cocrystals controlled by variable temperature ball milling N2 - Mechanochemistry offers a unique opportunity to modify or synthesize new crystal forms. Although the method is very promising, little is known about the mechanochemical means to control the synthesis of a solid form. Using an polymorphic organic cocrystal system, we show here that mechanochemistry can be used to obtain a polymorph transformation under the apparently conventional (thermal) transition point. T2 - Bessy User Meeting 2022 CY - Online meeting DA - 08.12.2022 KW - Mechanochemistry KW - Polymorphism KW - TRIS PY - 2022 AN - OPUS4-56473 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Karafiludis, Stephanos T1 - How do transition metal phosphates crystallise? N2 - Industrial and agricultural waste streams (waste waters, sludges, tailings etc.), which contain high concentrations of NH4+, PO43- and transition metals, are environmentally harmful due to their toxic pollutants. At the same time, phosphorus and selective transition metals such as Cobalt could be potentially depleted as a critical raw material due to the high demand and rapidly declining natural ore deposits. Therefore, due to simultaneous scarcity and abundance, the phosphorus and 3d metal recovery from agricultural, industrial, mining, or urban wastewaters have been an important factor in sustaining our global consumption and preservation of the natural environment. Typically, separate pathways have been considered to extract hazardous substances such as transition metals or phosphate, independently from each other. Here, we investigate the crystallization of transition metal phosphate (TMP) compounds (NH4MPO4∙6H2O, M3(PO4)2∙8H2O with M = Ni2+, Co2+, NixCo1-x2+ M-struvite and M-phosphate octahydrate) out of aqueous solutions, which allow for P, ammonia and metal co-precipitation. The precipitation of these compounds from industrial and agricultural waste waters has high potential as a P- and 3d metal recovery route. For this purpose, a detailed understanding of the crystallization process beginning from combination of solved ions and ending in a final crystalline product is required. Through adjusting the reaction conditions, the stability, crystallite size and morphology of the as-obtained TMPs could be controlled. Detailed investigations of the precipitation process in time using ex- and in-situ techniques provided new insights into their non-classical crystallization mechanism/crystal engineering of these materials. These TMPs involve transitional colloidal nanophases during the crystallization process. Over time, their complex amorphous framework changes significantly resulting simultaneously in an agglomeration and densification of the compound. After extended reaction times these colloidal nanophases condensed to a final crystal. However, the reaction kinetics of the formation of a final crystalline product and the lifetime of these intermediate phases vary significantly depending on the metal cation involved in the precipitation process. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P)-ratios, whereas Co tends to form Co-struvite and/or Co-phosphate octahydrate depending on the (M/P)-ratio. The mixed NixCo1-x system shows a significantly different crystallization behavior and reaction kinetics of the precipitation compared to the pure endmembers. The observed various degree of stability could be linked to the octahedral metal coordination environment in these compounds. The achieved level of control over the precipitates, is highly desirable for 3d- and P-recovery methods. Under this paradigm, the crystals can be potentially upcycled as precursor materials for (electro)catalytical applications. T2 - Granada Münster Discussion Meeting (GMDM) CY - Granada, Spain DA - 30.11.2022 KW - Struvite KW - Transition metal KW - Phosphates KW - Amorphous phases KW - Non-classical crystallization PY - 2022 AN - OPUS4-56478 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Exploring amorphous lewis-acidic zirconium chloro fluoride as a heterogeneous HF shuttle N2 - Owing to a growing shortage of fluorspar, a raw material used for producing fluorinated base chemicals, fluorspar has been named among the 30 critical raw materials in the EU. 1 However, the sustainable transfer of fluorine atoms from one molecule to another using heterogeneous catalysts has not yet been reported. Herein, we present the heterogeneous catalyst zirconium chloro fluoride (ZCF) that performs dehydrofluorination of a fluoroalkane and consecutive hydrofluorination of an alkyne at room temperature. T2 - InSynX Workshop 2023 CY - Sao Paulo, Brazil DA - 06.03.2023 KW - ZCF KW - Heterogeneous catalysis KW - C-F bond activation PY - 2023 AN - OPUS4-57228 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Metal fluoride surfaces by protonation with surface immobilized HF N2 - Lewis-acidic zirconium or chromium fluoride surfaces on different aluminium oxide or fluoride substrates. T2 - CRC 1349 Symposium 2021 CY - Berlin, Germany DA - 25.11.2021 KW - HF KW - Heterogeneous catalysis PY - 2021 AN - OPUS4-57226 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Linberg, Kevin T1 - Controlled Polymorphism by Elevated Temperature Ball Milling N2 - Mechanochemistry provides polymorphs that are difficult to obtain by conventional solution-based methods. Based on the nicotinamide and pimelic acid cocrystal, we demonstrated that the ball size, frequency, and temperature are essential parameters. Our results indicate that fine-tuning the energy input during a mechanochemical reaction can provide control over polymorphism. T2 - Bessy User Meeting 2023 CY - Berlin, Germany DA - 22.06.2023 KW - Mechanochemistry KW - Temperature KW - Cocrystal KW - Energy input KW - Polymorph PY - 2023 AN - OPUS4-57985 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - Zirconium chloro fluoride as catalyst for C-F bond activation and HF transfer of fluoroalkanes N2 - In this work, we successfully synthesized amorphous zirconium chloro fluoride (ZCF), which exhibits medium lewis acidity. In addition to investigating the local coordination sphere around the Zr atoms and the material properties, we were able to establish a catalytic behavior of ZCF in C-F bond activation reactions. We present a heterogeneous catalyst that performs dehydrofluorination of a fluoroalkane and consecutive hydrofluorination of an alkyne at room temperature. T2 - MC 16 CY - Dublin, Ireland DA - 03.07.2023 KW - ZCF KW - Heterogeneous catalysis KW - C-F bond activation PY - 2023 AN - OPUS4-58052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Heinekamp, Christian T1 - A fluorolytic sol-gel route to access an amorphous Lewis-acidic Zr fluoride catalyst N2 - The Kemnitz et al. developed a fluorolytic route to access metal fluorides 1 such as AlF3 2 and MgF2 3 which possess a high surface area. In aluminium-based systems, the synthetic approach led to amorphous xerogels that can be further converted into Lewis superacids.2 Still, despite zirconium oxide being described as a stronger Lewis acid than other metal oxides4 zirconium fluoride-based materials have only recently been reported or investigated. In this work we extend the class of amorphous Lewis acidic heterogeneous catalysts to an amorphous ZrF4 that is active in C-F bond activation. T2 - CRC 1349 Summer School 2023 CY - Berlin, Germany DA - 28.08.2023 KW - ZrF4 KW - Heterogeneous catalysis KW - C-F bond activation KW - Postfluorination PY - 2023 AN - OPUS4-58638 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hein-Paar, Jakob T1 - Spectroscopic Insights into the Reactivity of Energetic Materials N2 - Energetic materials (explosives, propellants, pyrotechnics, and gas generators; EM) release large amounts of energy when initiated by mechanical loading and have many technological applications including in energy storage and propulsion. The accidental initiation of an EM – particularly in the wrong setting – has the potential to be catastrophic. Unfortunately, there is little understood about what determines the sensitivity of a given EM. This poses severe restrictions on our ability to design new and safer EMs. Aiming to better understand the initiation mechanisms of EMs, we here investigate the reactivity of simple, isomorphous azides (MN3 M=Li, Na). Both metal azides contain the same explosophoric azido anions, but differ significantly in their reactivity, presumably owing to different bonding interactions between the anion and the metal cation. This interaction offers a promising probe for X-ray spectroscopy and quantum chemical simulations. In noting that mechanical initiation results from mechanical impact – with high local pressures – we are particularly interested in identifying how this bonding interaction changes as a function of pressure. This interaction offers a promising probe for X-ray spectroscopy and quantum chemical simulations. In noting that mechanical initiation results from mechanical impact – with high local pressures – we are particularly interested in identifying how this bonding interaction changes as a function of pressure. Here we show results from DFT simulations that indicate a shift in electronic structure and changes in the metal-azide bond with increasing pressure, which is further investigated through experimental XAS spectra. Together, our results show promising insights into the behaviour of simple metal azide EMs. T2 - SXR2023 - Principles of Functionality From Soft X-Ray Spectroscopy CY - Berlin, Germany DA - 11.09.2023 KW - Energetic materials PY - 2023 AN - OPUS4-58824 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gugin, Nikita T1 - ZIF-8-Based Biocomposites via Reactive Extrusion: Towards Industrial-Scale Manufacturing N2 - Mechanochemistry offers a solvent-free, sustainable alternative to conventional synthesis of metal-organic framework (MOF) biocomposites, which hold great promise for applications in drug delivery, biocatalysis, and biosensing,[1] yet the field remains limited to batch-type, gram-scale processes that restrict industrial application. To overcome these limitations, we present a scalable solid-state method for producing MOF-based biocomposites via continuous reactive extrusion. The process begins with rapid model reactions using hand-mixing[2] to encapsulate a variety of biomolecules into zeolitic imidazolate framework-8 (ZIF-8), including proteins, carbohydrates, and enzymes, thereby enabling rapid screening and optimization of reaction conditions. The mild synthesis conditions preserve the catalytic activity of glucose oxidase, confirming the suitability of the method to sensitive biomaterials. Building on this, we translated the batch protocol to twin-screw extrusion,[3] enabling continuous and scalable synthesis of biocomposites such as bovine serum albumin (BSA)@ZIF-8 with tunable protein content. The extrusion process yielded highly crystalline, porous materials with protein loadings of up to 26 wt% and encapsulation efficiencies as high as 96%. The production rate reached 1.2 kg d⁻¹, significantly exceeding previously reported continuous methods.[4] To demonstrate the industrial viability of the method, we extended the approach to produce shaped ZIF-8 monoliths loaded with hyaluronic acid (HA) in a single-step extrusion. These monoliths retained their structural integrity during washing and released HA without measurable degradation, as confirmed by size-exclusion chromatography. Our study opens new avenues for the industrial implementation of MOF biocomposites and establishes reactive extrusion as a robust platform for their scalable synthesis and shaping, expanding the toolkit for drug delivery and biocatalytical applications. T2 - Tag der Chemie 2025 CY - Berlin, Germany DA - 03.07.2025 KW - Mechanochemistry PY - 2025 AN - OPUS4-63802 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Ryll, Tom William T1 - In-situ analysis of nucleation processes – case study: calcium sulfate N2 - In this project we investigate nucleation pathways by utilizing synchrotron-XRD and running a case-study on calcium sulfate phases. To accomplish this, we developed a modular automation setup for reactions in solution to run synthesis and control reaction conditions. So far we successfully characterized the recycling process of gypsum and are now investigating the formation of anhydrite. T2 - BESSY@HZB User Meeting CY - Berlin, Germany DA - 02.12.2025 KW - Recycling KW - Gypsum KW - Synchrotron-X-ray-diffraction KW - Raman-spectroscopy KW - Automation PY - 2025 AN - OPUS4-65344 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -