TY - JOUR A1 - Wilke, Manuel A1 - de Oliveira Guilherme Buzanich, Ana A1 - Reinholz, Uwe A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - The structure and in situ synthesis investigation of isomorphic mononuclear molecular metal phenylphosphonates N2 - We describe a fast and effective synthesis for molecular metal phosphonates. Isomorphic compounds [M(II)(HO₃PPh)₂(H₂O₃PPh)₂(H₂O)₂] (M = Mn (1), Co (2), Ni (3); Ph = C₆H₅) were obtained by grinding. The complexes are mononuclear compounds containing neutral and monodeprotonated phenylphosphonic acid and water as ligands. The crystal structures were determined using powder X-ray diffraction (PXRD) data and validated by extended X-ray absorption fine structure (EXAFS) data. Combined synchrotron XRD measurements and Raman spectroscopy were conducted for investigating the reactions in situ. Based on these data, the intermediates were characterized and the formation mechanism was derived. KW - Mechanochemistry KW - Metal phosphonate KW - In situ KW - XRD PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-363944 DO - https://doi.org/10.1039/c6dt00787b SN - 1477-9226 SN - 1477-9234 SN - 1364-5447 VL - 45 IS - 23 SP - 9460 EP - 9467 AN - OPUS4-36394 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wilke, Manuel A1 - Batzdorf, Lisa A1 - Fischer, Franziska A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - Cadmium phenylphosphonates: preparation, characterisation and in situ investigation N2 - The successful mechanochemical syntheses of three cadmium phenylphosphonates indicates that mechanochemistry is ideally suited for synthesizing metal phosphonates. With this powerful synthesis tool it is possible to synthesize rapidly and efficiently both known and novel phosphonates. The Crystal structures of the two new compounds, and, were solved from PXRD data. They contain monodeprotonated phenylphosphonate and neutral phenylphosphonic acid ligands. The synthesis pathways of all three compounds were investigated in situ. A diffusion mechanism is corroborated by our findings. Intermediates could be detected and identified. The kinetically favored product (3) could always be detected during the syntheses. The thermodynamic stability of the compounds and the stoichiometric ratio of the starting materials are the two directing factors for the synthesis of the final products. KW - Mechanochemistry KW - Metal phosphonate KW - In situ KW - MOF KW - XRD PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-363322 DO - https://doi.org/10.1039/c6ra01080f SN - 2046-2069 VL - 6 IS - 42 SP - 36011 EP - 36019 PB - Royal Soc Chemistry CY - Cambridge, UK AN - OPUS4-36332 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wilke, Manuel A1 - Klimakow, Maria A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Fast and efficient synthesis of a host guest system: a mechanochemical approach N2 - An unusually fast and effective synthesis procedure for a host guest system consisting of a metal organic framework (MOF) and a polyoxometalate (POM) is described. The material was synthesised mechanochemically and the evolution of the structure was monitored ex and in situ using synchrotron X-ray diffraction (XRD). KW - Mechanochemistry KW - MOF KW - in situ PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-354910 UR - http://pubs.rsc.org/en/Content/ArticleLanding/2016/CE/C5CE01868D#!divAbstract DO - https://doi.org/10.1039/C5CE01868D VL - 18 IS - 7 SP - 1096 EP - 1100 AN - OPUS4-35491 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Michalchuk, Adam A1 - Emmerling, Franziska T1 - Time-Resolved InSitu Monitoring of Mechanochemical Reactions N2 - Mechanochemical transformations offer environmentally benign synthesis routes, whilst enhancing both the speed and selec-tivity of reactions. In this light, mechanochemistry promises to trans-form the way in which chemistry is done in both academia and indus-try but is greatly hindered by a current lack in mechanistic understand-ing. The continued development and use of time-resolved in situ(TRIS) approaches to monitor mechanochemical reactions provides a new dimension to elucidatethese fascinating transformations. We here discuss recent trends in method development that have pushed the boundaries of mechanochemical research. New features of mech-anochemical reactions obtained by TRIS techniques are subse-quently discussed, shedding light on how different TRISapproaches have beenused. Emphasis is placed on the strength of combining complementary techniques. Finally, we outline our views for the po-tential of TRIS methods in mechanochemical research, towards es-tablishing a new, environmentally benign paradigm in the chemical sciences KW - Mechanochemistry KW - Material synthesis KW - Green chemistry PY - 2022 DO - https://doi.org/10.1002/anie.202117270 SN - 1433-7851 SP - 1 EP - 15 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54321 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Prinz, Carsten A1 - Scholz, Gudrun A1 - Kemnitz, Erhard A1 - Emmerling, Franziska T1 - Ca-, Sr-, and Ba-Coordination polymers based on anthranilic acid via mechanochemistry N2 - Ca-, Sr-, and Ba-Based coordination polymers (CPs) were prepared mechanochemically by milling metal-hydroxide samples with anthranilic acid (oABAH). {[Ca(oABA)2(H2O)3]}n consists of one-dimensional polymeric chains that are further connected by a hydrogen-bonding network. {[Sr(oABA)2(H2O)2]·H2O}n is a one-dimensional CP in which water molecules bridge Sr2+ ions and increase the dimensionality by building an extended network. {[Ba(oABA)2(H2O)]}n crystallizes as a two-dimensional CP comprising one bridging water molecule. The cation radii influence the inorganic connectivity and dimensionality of the resulting crystal structures. The crystal structures were refined from powder X-ray diffraction data using the Rietveld method. The local coordination environments were studied via extended X-ray absorption fine structure (EXAFS) measurements. The compounds were further characterized using comprehensive analytical methods such as elemental analysis, thermal analysis, MAS NMR, imaging, and dynamic vapor sorption (DVS) measurements. Compounds 1, 2, and 3 exhibit small surface areas which decrease further after thermal annealing experiments. All compounds exhibit a phase transformation upon heating, which is only reversible in 3. KW - Mechanochemistry KW - XRD PY - 2019 DO - https://doi.org/10.1039/c9dt00991d SN - 1477-9226 SN - 1477-9234 VL - 48 IS - 19 SP - 6513 EP - 6521 PB - Royal Society of Chemistry AN - OPUS4-48014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoque, Maroof Arshadul T1 - Mechanochemically synthesized COF for PFAS adsorption N2 - Since the 1950s, per- and polyfluoroalkyl substances (PFAS) have been widely used in a range of consumer products, including clothing, paints, cookware and fast-food packaging. Properties such as high thermal resistance and water and oil repellency contribute to their wide usage. After decades of production, these substances have eventually found their way into our drinking water. Given the adverse effects of PFAS molecules on human health, the removal of these substances from our drinking water is a matter of urgency.1 This study employs the use of materials known as covalent organic frameworks (COFs) to adsorb PFAS molecules from an aqueous medium. COFs are crystalline, highly porous, two- or three-dimensional polymers with tunable topology and functionalities.² For the purposes of this study, a COF was synthesised using 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 1,3,5-triformylbenzene (TFB) via a mechanochemical process. Mechanochemistry represents a green synthesis method that uses mechanical energy to initiate chemical reactions, as opposed to using harmful solvents and heat.3 Adsorption tests were carried out to test the effectiveness of the material in question against PFAS. The COF was exposed to a solution of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid PFOS). Following a 13-hour period, it was observed that 90% of PFOA and 99% of PFOS had been adsorbed by the COF. Most of the adsorption appeared to have occurred within the first 10 minutes of exposure. It can therefore be concluded that the TAPB-TFB COF is a promising material for the adsorption of PFAS molecules. T2 - Adlershofer Forschungsforum 2024 CY - Berlin, Germany DA - 11.11.2024 KW - Covalent organic framework KW - Mechanochemistry KW - PFAS KW - In situ Xray diffraction PY - 2024 AN - OPUS4-61808 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Metal phosphonates as proton conductors and ORR catalysts N2 - Metal phosphonates are promising materials for applications in fuel cells, due to their high proton conductivity and higher chemical and thermal stability compared to the industry standard (e.g. Nafion®). Additionally, metal phosphonates are precursors to porous carbon materials with evenly distributed centers for ORR catalysis. As a fast and sustainable synthesis, mechanochemistry is the synthesis method of choice. Thorough characterization is carried out by XRD, MAS-NMR, XAS, BET, and DVS. T2 - 2nd European Workshop on Metal Phosphonates CY - Berlin, Germany DA - 24.09.2019 KW - Phosphonates KW - Proton cunductor KW - Oxygen reduction reaction KW - Catalysis KW - Mechanochemistry PY - 2019 AN - OPUS4-50257 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wilke, Manuel A1 - Bach, S. A1 - Gorelik, T. A1 - Kolb, U. A1 - Tremel, W. A1 - Emmerling, Franziska T1 - Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution N2 - Divalent metal phosphonates are promising hybrid materials with a broad field of application. The rich coordination chemistry of the phosphonate linkers enables the formation of structures with different dimensionalities ranging from isolated complexes and layered structures to porous frameworks incorporating various functionalities through the choice of the building blocks. In brief, metal phosphonates offer an interesting opportunity for the design of multifunctional materials. Here, we provide a short review on the class of divalent metal phosphonates discussing their syntheses, structures, and applications. We present the advantages of the recently introduced mechanochemical pathway for the Synthesis of divalent phosphonates as a possibility to generate new, in certain cases metastable compounds. The benefits of in situ investigation of synthesis mechanisms as well as the implementation of sophisticated methods for the structure analysis of the resulting compounds are discussed. KW - Metal phosphonate KW - Mechanochemistry PY - 2017 DO - https://doi.org/10.1515/zkri-2016-1971 SN - 2194-4946 SN - 2196-7105 VL - 232 IS - 1-3 SP - 209 EP - 222 PB - De Gruyter AN - OPUS4-40003 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Franziska A1 - Lubjuhn, Dominik A1 - Greiser, Sebastian A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Supply and demand in the ball mill: competitive cocrystal reactions N2 - The stability of different theophylline cocrystals under milling conditions was investigated by competitive cocrystal reactions. To determine the most stable cocrystal form under milling conditions, the active pharmaceutical ingredient theophylline was either ground with two similar coformers (benzoic acid, benzamide, or isonicotinamide), or the existing theophylline cocrystals were ground together with a competitive coformer. All competitive reactions were investigated by in situ powder X-ray diffraction disclosing the formation pathway of the milling processes. On the basis of these milling reactions, a stability order (least to most stable) was derived: tp/bs < tp/ba < tp/ina < bs/ina. KW - Mechanochemistry KW - Cocrystal KW - Milling PY - 2016 DO - https://doi.org/10.1021/acs.cgd.6b00928 SN - 1528-7483 SN - 1528-7505 VL - 16 IS - 10 SP - 5843 EP - 5851 AN - OPUS4-38097 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fischer, Franziska A1 - Greiser, Sebastian A1 - Peifer, Dietmar A1 - Jäger, Christian A1 - Rademann, K. A1 - Emmerling, Franziska T1 - Mechanochemically Induced Conversion of Crystalline Benzamide Polymorphs by Seeding N2 - Benzamide has been known for its polymorphism for almost 200 years.Three polymorphic forms are described. To date,itwas only possible to crystallizeametastable form in amixture together with the thermodynamically most stable form I. Acomplete transformation of form Iinto the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X-ray diffraction. KW - Nicotinamide KW - Benzamide KW - In situ reactions KW - Mechanochemistry KW - Polymorphs PY - 2016 DO - https://doi.org/10.1002/anie.201607358 VL - 128 IS - 46 SP - 14493 EP - 14497 PB - WILEY-VCH CY - Weinheim AN - OPUS4-38472 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - May the Force be with you - Mechanochemical syntheses studied in situ N2 - Mechanochemistry is a fast and efficient method applicable for the synthesis of new organic, metal-organic, and inorganic compounds. The direct monitoring of milling reactions is still challenging. The underlying reaction mechanisms remain often unclear. In the last years, have established a tandem in situ approach for investigating mechanochemical reactions using time-resolved in situ XRD coupled with Raman spectroscopy. Here, we present an in situ coupling of synchrotron XRD, Raman spectroscopy, and thermography allowing the observation of mechanochemical reactions in real time. Information on the crystalline, molecular, and temperature state of the materials during grinding could be collected. The chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. Furthermore, the presented setup allows the detection of crystalline, amorphous, eutectic as well as liquid intermediates. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses. T2 - Seminar Universität Montpellier CY - Montpellier, France DA - 24.01.2019 KW - Mechanochemistry KW - In situ PY - 2019 AN - OPUS4-47261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martins, I. A1 - Carta, M. A1 - Haferkamp, Sebastian A1 - Feiler, Torvid A1 - Delogu, F. A1 - Colacino, E. A1 - Emmerling, Franziska T1 - Mechanochemical N‑Chlorination Reaction of Hydantoin: In Situ Real-Time Kinetic Study by Powder X‑ray Diffraction and Raman Spectroscopy N2 - Mechanochemistry has become a valuable tool for the synthesis of new molecules, especially in the field of organic chemistry. In the present work, we investigate the kinetic profile of the chlorination reaction of N-3-ethyl-5,5-dimethylhydantoin (EDMH) activated and driven by ball milling. The reaction has been carried out using 2 mm, 4 mm, 5 mm, 6 mm, and 8 mm ball sizes in a new small custom-made Perspex milling jar. The Crystal structure of the starting material EDMH and the 1-chloro-3-ethyl5,5′-dimethyl hydantoin (CEDMH) chlorination product was solved by single-crystal X-ray diffraction. The reaction was monitored, in situ and in real time, by both powder X-ray diffraction (PXRD) and Raman spectroscopy. Our kinetic data show that the reaction progress to equilibrium is similar at all milling ball sizes. The induction period is very short (between 10 and 40 s) when using 4 mm, 5 mm, 6 mm, and 8 mm balls. For the reaction performed with a 2 mm ball, a significantly longer induction period of 9 min was observed. This could indicate that an initial energy accumulation and higher mixing efficiency are necessary before the reaction starts. Using different kinetic models, we found that the amount of powder affected by critical loading conditions during individual impacts is significantly dependent on the ball size used. An almost linear correlation between the rate of the chemical transformations and the ball volume is observed. KW - Mechanochemistry KW - In situ real-time monitoring KW - N-Chlorination KW - Kinetics KW - Hydantoin KW - Powder X-ray diffraction KW - Raman spectroscopy PY - 2021 DO - https://doi.org/10.1021/acssuschemeng.1c03812 VL - 9 IS - 37 SP - 12591 EP - 12601 AN - OPUS4-53541 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Souza, B. A1 - Chauque, S. A1 - de Oliveira, P. A1 - Emmerling, Franziska A1 - Torresi, R. T1 - Mechanochemical optimization of ZIF-8/Carbon/S8 composites for lithium-sulfur batteries positive electrodes N2 - The application of lithium-sulfur (Li-S) batteries is still limited by their rapid capacity fading. The pulverization of the sulfur positive electrode after the lithiation and the consequence dissolution of long chain polysulfides in organic solvents lead to the shuttle effect. To address these issues, here we report the mechanochemical preparation of ZIF-8 (Zeolitic Imidazole Framework-8)-based composites as sulfur hosts for positive electrodes in Li-S batteries. We studied different methods for the incorporation of conductive carbon. Also, the replacement of Zn2+ metal centers by other bivalent metals (Cu2+, Co2+ and Ni2+), enabled the preparation of other ZIF-8-based materials. The positive electrode ZIF-8/C/S8 showed initial discharges of 772 mA h g−1 while the pristine one, ZIF-8/S8, displayed 502 mA h g−1. The enhanced performance of 54% for ZIF-8/C/S8 indicates that the direct mechanochemical synthesis of ZIF-8 with conductive carbon is beneficial at initials charge/discharge process in comparison to traditional slurry preparation (ZIF-8/S8). Also, the Li2S6 absorption tests shows 87% of discoloration with ZIF-8/C/S8, confirming the better polysulfides absorption. KW - Lithium-sulfur battery KW - Metal organic frameworks KW - ZIF-8 KW - Mechanochemistry PY - 2021 DO - https://doi.org/10.1016/j.jelechem.2021.115459 VL - 896 SP - 115459 PB - Elsevier B.V. AN - OPUS4-53542 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Fluorine Modified ZIF 8 for Electrochemical Catalysis: Where does the Fluorine go? N2 - Carbonization of fluorinated metal-organic frameworks (MOFs) should yield fluorinated nitrogen- and metal-doped carbons (F-NMCs), which are a combination of NMCs and fluorinated carbons, each promising electrocatalysts on their own. We synthesized two polymorphs of a fluorinated MOF by mechanical ball mill grinding, and carbonized them to yield potential electrocatalyt materials. The catalytical activity towards the oxygen reduction reaction (ORR) was examined, finding good activites. Simulations from a theoretic model helped assesing the stability of proposed catalytic sites and understanding the measured activites towards the ORR catalysis. T2 - Online symposium of the CRC 1349 "fluorine-specific interactions" CY - Online meeting DA - 29.06.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs KW - Computational chemistry PY - 2021 AN - OPUS4-53538 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Synthesis and characterization of fluorinated Co-Zn-Zeolitic imidazole frameworks for catalysis of the oxygen reduction reaction N2 - The oxygen reduction reaction (ORR) is a common process in a variety of electrochemical devices, like fuel cells and metal air batteries. The sluggish kinetics of the ORR require an electrocatalyst to pass this bottleneck.[1] Currently, the most used catalytical systems are platinum-based, with several drawbacks, such as the high cost, low availability, and deactivation by CO poisoning.[2] Efforts are made to develop efficient, durable and low cost catalysts to promote the commercialization of fuel cells. Non-precious metal catalysts are promising candidates for efficient ORR catalysis. It has been shown that pyrolyzing metal organic frameworks (MOFs) under inert conditions yields carbon-rich materials, with evenly distributed metal sites, which possess promising electrocatalytic activity.[3] One widely used type of MOF as ORR catalyst precursors is the zeolitic imidazole framework (ZIF) where metal cations are linked through imidazolebased ligands. Herein we report the mechanochemical synthesis, structural analysis and of Co-doped ZIF-8 (Zn), as well as its fluorinated counterpart Co-doped CF3 -ZIF-8 (Zn). The samples showed electrochemical performance comparable to platinum after carbonization for 1h at temperatures ranging between 850 – 1000°C. T2 - 15th International conference on materials chemistry (MC15) CY - Online meeting DA - 12.07.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs PY - 2021 AN - OPUS4-53539 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - The Effect of Fluorine on Catalysts for the Oxygen Reduction Reaction obtained from Metal Organic Frameworks N2 - The oxygen reduction reaction (ORR) – an important reaction in electrochemical devices, such as fuel cells - is characterized by its sluggish kinetics and therefore requires catalysis. The industry currently relies on platinum as a catalyst, although it is scarce and expensive, hindering the commercial breakthrough of fuel cells in automotive applications. Platinum-free catalysts on basis of nitrogen- and metal doped carbons (NMCs) and fluorinated carbons are promising materials to replace platinum-based catalysts for the ORR. In this work we prepared six metal-organic frameworks (MOFs) by mechanical ball mill grinding and studied their formation by in-situ powder X-ray diffraction. Furthermore, the samples were carbonized under controlled conditions (900°C, 1h, N2-atmosphere) to yield carbon materials, that were employed in ORR-electrocatalysis. The effect of Co-doping and fluorination was systematically studied and outstanding ORR activity was found for the catalyst prepared from the Co-doped fluorinated ZIF-8. T2 - International Symposium on Fluorine-specific interactions CY - Berlin, Germany DA - 27.09.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs PY - 2021 AN - OPUS4-53533 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rautenberg, Max T1 - Fluorination and co-doping of ZIF-8 by ball mill grinding for efficient oxygen reduction electrocatalysis N2 - The oxygen reduction reaction (ORR) is a common process in a variety of electrochemical devices, like fuel cells and metal air batteries. The sluggish kinetics of the ORR require an electrocatalyst to pass this bottleneck.[1] Currently, the most used catalytical systems are platinum-based, with several drawbacks, such as the high cost, low availability, and deactivation by CO poisoning.[2] Efforts are made to develop efficient, durable and low cost catalysts to promote the commercialization of fuel cells. Non-precious metal catalysts are promising candidates for efficient ORR catalysis. It has been shown that pyrolyzing metal organic frameworks (MOFs) under inert conditions yields carbon-rich materials, with evenly distributed metal sites, which possess promising electrocatalytic activity.[3] One widely used type of MOF as ORR catalyst precursors is the zeolitic imidazole framework (ZIF) where metal cations are linked through imidazole-based ligands. Their porous nature is partially retained after carbonization, making MOFs very suitable precursor materials. Herein we report the mechanochemical synthesis and structural analysis of Co-doped ZIF-8 (Zn), as well as two polymorphs (dense and prorous) of fluorinated Co-doped CF3-ZIF-8 (Zn). The samples showed electrochemical performance comparable to platinum after carbonization for 1 h at temperatures ranging between 850 – 1000°C. T2 - XXV General Assembly and Congress of the International Union of Crystallography - IUCr 2021 CY - Prague, Czech Republic DA - 14.08.2021 KW - PGM-free catalyst KW - Oxygen Reduction Reaction KW - Mechanochemistry KW - MOFs PY - 2021 AN - OPUS4-53535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Linberg, Kevin T1 - Tipping the Energy Scales to Control Mechanochemical Polymorphism N2 - Control of ball milling conversions is required before the full potential of mechanochemical processing can be realized. It is well known that many parameters affect the outcome of mechanochemical polymorphism, but the energy of ball milling itself is often overlooked. We show here how this parameter alone can exert a significant influence on the polymorphic outcome of ball mill grinding by allowing the selective isolation of two polymorphic forms in their pure form under the same grinding conditions. Furthermore, we show how apparent mechanochemical equilibria can be deceptive. Our results clearly demonstrate the need for careful design and interpretation of ball milling experiments beyond current thinking. T2 - SALSA make and measure CY - Online meeting DA - 16.09.2021 KW - Mechanochemistry KW - Energy KW - Polymorph KW - Cocrystal PY - 2021 AN - OPUS4-53293 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - New insights in formation pathways: in situ investigations of mechanochemical reactions N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals.1 The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms.2,3 We recently introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. In this contribution, I will discuss our recent results investigating the formation of (polymorphic) cocrystals and metal phosphonates.4 First investigations of a mechanochemical synthesis under controlled temperature which allow determining the activation barrier are presented. Furthermore, in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat.5 Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds. T2 - International Conference on Mechanochemistry and Mechanical Alloying, INCOME 2017 CY - Kosice, Slovakia DA - 03.09.2017 KW - Mechanochemistry KW - In situ PY - 2017 AN - OPUS4-43564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kulla, Hannes T1 - In situ investigations of a mechanochemical cocrystal formation by X-ray diffraction for two different milling jar materials N2 - Mechanochemistry has become a valuable method for the synthesis of new materials, especially for pharmaceutical cocrystals. The Advantages of fast reactions in high purity and yield face a lack of understanding the underlying mechanism. Therefore, in situ setups to study mechanochemical reactions have been established. Herein, we present an in situ investigation of the mechanochemical cocrystal formation of pyrazinamide (PZA) with pimelic acid (PM) using synchrotron XRD. Two new polymorphs of PZA:PM (1:1) were synthesized by milling the starting materials in milling jars of different materials. While Form I is only obtained using a steel jar, Form II can be obtained purely in jars made of Perspex. In situ XRD experiments reveal a direct formation of Form II in Perspex and an intermediate formation of Form II in steel jars converting to Form I upon further grinding. Heating experiments and DFT calculations predict that Form II is the thermodynamically more stable polymorph. Therefore, the reaction progress in the steel jar contradicts Ostwald’s rules of stages as the more stable Form II converts into the metastable Form I. Hence, mechanochemistry offers the possibility to synthesize new materials that cannot be obtained using conventional methods. T2 - Adlershofer Forschungsforum 2017 CY - HU-Berlin, Erwin-Schrödinger Zentrum, Germany DA - 10.11.2017 KW - Cocrystal KW - Mechanochemistry KW - Polymorph KW - In situ KW - Milling PY - 2017 AN - OPUS4-42956 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tumanov, I. A1 - Tumanov, E. A1 - Michalchuk, Adam T1 - Ball size or ball mass – what matters in organic mechanochemical synthesis? N2 - Ball mass is an important parameter that is known to have an influence on the outcome of a mechanochemical reaction induced by ball-milling. A standard way of modifying the ball mass is to change the size of the ball made of the same material. In this case, however, a change in mass is accompanied by a simulatneous change in the ball size. It is therefore not possible to disentangle the effects of mass and Surface area in these cases. In the present work we report the results of experiments with specially designed and manufactured balls in which (1) milling ball mass is held constant, but their size differs, and (2) the ball mass is altered, with the diameter of the milling ball being held constant. Using the cocrystallisation of theophylline + nicotinamide as a case study it was found that both diameter and ball mass play crucial roles in determining the rate of a mechanochemical reaction. For comparison, we have also used milling balls with the same size (different mass), and others with the same mass (different size) made of different materials, as would be “traditional”. It was found that, despite having the same size, the lightest milling ball (nylon) was the most efficient in initiating the co-crystallisation, presumably due to the sorption of EtOH. Hence, the results of this manuscript also demonstrate how milling ball material can in fact be the most influential parameter, and potentially counterintuitive to classical mechanics. KW - Mechanochemistry KW - XRD PY - 2019 DO - https://doi.org/0.1039/c8ce02109k VL - 21 SP - 2174 EP - 2179 PB - RSC Royal Society of Chemistry AN - OPUS4-47851 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - New insights in cocrystal formations: in situ investigations of mechanochemical syntheses N2 - Mechanochemistry is increasingly used for synthesizing soft matter materials including metal organic compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. Time-resolved in situ investigations of milling reactions provide direct insights in the underlying mechanisms. We introduced a setup enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. We discuss our recent results investigating the formation of (polymorphic) cocrystals. First investigations of a mechanochemical synthesis under controlled temperature which allow determining the activation barrier are presented.6 Furthermore, X-ray diffraction and in situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases as a result of the reaction heat. Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds. T2 - CSEC Seminar University of Edinburgh CY - Edinburgh, Scotland DA - 16.05.2019 KW - Mechanochemistry KW - Acoustic levitation KW - In situ PY - 2019 AN - OPUS4-48098 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Haferkamp, Sebastian A1 - Emmerling, Franziska T1 - In situ investigations of mechanochemical reactions N2 - Mechanochemistry paves the way to simple, fast, and green syntheses. Despite considerable effort, there remains a lack in understanding of the underlying mechanisms. In situ investigations help to understand these mechanisms, which occur during a mechanochemical reaction. Here we present a universal strategy for simultaneous real-time in situ analysis, combining X-ray diffraction, Raman spectroscopy, and thermography. The potential of our approach is shown for different model reactions. T2 - ANAKON 2019 CY - Münster, Germany DA - 25.03.2019 KW - In situ KW - Mechanochemistry KW - Milling PY - 2019 AN - OPUS4-47701 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - May the force be with you - in situ investigation of mechanochemical reactions N2 - The past decade has seen a reawakening of solid-state to chemical synthesis, driven by the search for new, cleaner synthetic methodologies. Mechanochemistry has advanced to a widely applicable technique. T2 - SALSA's "Make and Measure 2019 CY - Berlin, Germany DA - 25.10.2019 KW - Mechanochemistry KW - Metal–organic frameworks PY - 2019 AN - OPUS4-50138 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanochemistrry - a time resolved perspective on unconventional crystallization N2 - Green chemsistry apporoach for the synthesis of metal organic frameworks. T2 - IFW BAM Workshop CY - Berlin, Germany DA - 25.11.2019 KW - Mechanochemistry KW - XRD KW - Metal-organic-frameworks PY - 2019 AN - OPUS4-50110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Linberg, Kevin T1 - Insights into Mechanochemical Reactions using High Pressure XRD and DFT Simulations N2 - The reactivity of organic solids under mechanochemical conditions remains very little understood, though many processes have been found empirically. Importantly, it is not well understood how mechanical treatment induces experimentally observed chemical transformations, and if the elevated pressures arising at the point of impact can play a role in the transformation. To understand this aspect of the mechanochemical reactions, the same compounds need to be explored under high pressure conditions. As a model system, we considered the reaction between the bis(4-chlorophenyl) disulfide and bis(2-nitrophenyl) disulfide. A powder mixture of these two compounds is known to undergo a disulfide exchange reaction under ball milling conditions. Using a combination of X-ray powder diffraction and dispersion-corrected density functional theory calculations, we investigated how this binary solid system behaves at elevated pressures and whether pressure alone can explain its mechanochemical reactivity. T2 - International Scientific Student Conference 2021 CY - Online meeting DA - 12.04.2021 KW - Mechanochemistry KW - High Pressure KW - Density-functional theory PY - 2021 AN - OPUS4-52494 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Cocrystal polymorphs & Mechanochemistry - Mechanism & Kinetics N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new crystal forms. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of mechanochemical reactivity and selectivity. Control over ball milling transformations is needed before the transformative potential of mechanochemical processing can be realized. Different analytical methods and their combinations have been developed for the time-resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of polymorphic cocrystals thereby elucidating the influence of milling parameters (solvent, temperature, time) and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes. T2 - 33th European Crrystallography Meeting CY - Versailles, France DA - 23.08.2022 KW - Mechanochemistry KW - Cocrystals KW - Kinetics KW - Polymorphs PY - 2022 AN - OPUS4-55586 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Cocrystal polymorphs & Mechanochemistry - Mechanism & Kinetics N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new crystal forms. Different milling parameters are known to affect the mechanisms and rates of product formation: milling frequency, milling time, filling degree of the milling jar, ball diameter and vessel size, degree of milling ball filling, and material of jars. The increasing interest in mechanochemistry is contrasted by a limited mechanistic understanding of mechanochemical reactivity and selectivity. Control over ball milling transformations is needed before the transformative potential of mechanochemical processing can be realized. Different analytical methods and their combinations have been developed for the time-resolved in situ monitoring of mechanochemical transformations, including powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography. Here we will discuss our recent results investigating the formation of polymorphic cocrystals thereby elucidating the influence of milling parameters (solvent, temperature, time) and reaction sequences on the formation mechanism and kinetics. For the mechanochemical chlorination reaction of hydantoin normalizing the kinetic profiles to the volume of the milling ball showed clearly that milling reaction kinetics are conserved. Here physical kinetics dominate reaction rates in a ball-milling transformation. Attempting to interpret such kinetics in purely chemical terms risk misinterpreting the results. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes. T2 - 3rd CEFMC meeting CY - Kashmir, India DA - 31.08.2022 KW - Mechanochemistry KW - Crystal Engeneering PY - 2022 AN - OPUS4-55641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - In situ analysis of mechanochemical reactions using combined X-ray diffraction and Raman spectroscopy N2 - Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. Besides well-known MOFs like ZIF-8, the formation process of new metal phosphonates and model cocrystals could be studied in detail. The syntheses pathway of the different compounds could be revealed. The results prove that the presented method combination is applicable for a wide range of materials and will provide the necessary understanding to tune and optimize mechanochemically synthesized compounds. T2 - 3oth Meeting of the European Crystallographic Association CY - Basel, Switzerland DA - 28.08.2016 KW - Mechanochemistry KW - In situ PY - 2016 AN - OPUS4-38363 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kabelitz, Anke T1 - Direkt in-situ analysis of milling reactions: a look in the blackbox N2 - Mechanochemistry is increasingly used for synthesizing various materials. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained by in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup combining in situ synchrotron XRD and Raman spectroscopy. This combination allows to study milling processes comprehensively on the level of the molecular and crystalline structure and thus obtaining reliable data for mechanistic studies. The formation process of MOFs, metal phosphonates and model cocrystals could be studied in detail. The results prove that the presented method combination is applicable for a wide range of materials and will provide the necessary understanding to tune and optimize mechanochemically synthesized compounds. T2 - MS&T 2016: Mechanochemical Synthesis and Reactions in Materials Science CY - Salt Lake City, USA DA - 24.10.2016 KW - Mechanochemistry KW - In situ KW - Mechanistic studies PY - 2016 AN - OPUS4-38174 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Fischer, Franziska T1 - Polymorphism of mechanochemically synthesized Cocrystals: an in situ study N2 - In situ investigations using PXRD coupled with Raman spectroscopy permit the evaluation of the formation pathways of milling reactions. The liquid-assisted grinding cocrystallisation of theophylline with benzamide leading to polymorphic compounds was investigated. The dipole moment of the solvent used in the synthesis determines the structure of the polymorphic product. A detailed investigation allows determining the kinetically and thermodynamically favored product. In situ observations of the formation pathway during the grinding process of both polymorphs show that the thermodynamically favored cocrystal is formed in a two-step mechanism with the kinetic cocrystal as intermediate. The evaluation of the mechanochemical formation pathways reveals the importance of in situ investigations for an in depth understanding of mechanochemical synthesis mechanisms. Our study demonstrates that the choice of the solvent in the LAG synthesis is decisive for the controlled formation of a desired polymorphic final product. T2 - CGOM/ BACG 47th Annual British Association of Crystal Growth Conference CY - Leeds, UK DA - 28.06.2016 KW - Cocrystal KW - Mechanochemistry KW - Milling PY - 2016 AN - OPUS4-36764 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Emmerling, Franziska A1 - Tumanov, N. A1 - Tumanova, N. A1 - Fischer, Franziska A1 - Morelle, F. A1 - Ban, V. A1 - Robeyns, K. A1 - Filinchuk, Y. A1 - Wouters, J. A1 - Leyssens, T. T1 - Exploring polymorphism and stoichiometric diversity in naproxen/proline cocrystals N2 - We present naproxen/proline cocrystals discovered when combining enantiopure and racemic naproxen and proline. Using liquid-assisted grinding as the main method to explore the variety of crystal forms in this system, we found 17 cocrystals, of which the structures of only four of them were previously known. The naproxen/proline system exhibited multiple polymorphs of 1 : 1 stoichiometry as well as more rare cocrystals with 1 : 2 and 2 : 3 stoichiometries, two cocrystal hydrates and one cocrystal solvate. In situ ballmilling, used to monitor liquid-assisted grinding reactions, revealed that the solvent dictates the reaction intermediates even if the final reaction product stays the same. Synchrotron X-ray diffraction data collected in situ upon heating allowed us to monitor directly the phase changes upon heating and gave access to pure diffraction patterns of several cocrystals, thus enabling their structure determination from powder X-ray diffraction data; this method also confirmed the formation of a conglomerate in the RS-naproxen/DL-proline system. Proline in cocrystals kept its ability to form charge-assisted head-to-tail N-H⋯O hydrogen bonds, typical of pure crystalline amino acids, thus increasing the percentage of strong chargeassisted interactions in the structure and consequently providing some of the cocrystals with higher melting points as compared to pure naproxen. The majority of drugs are chiral, and hence, these data are of importance to the pharmaceutical industry as they provide insight into the challenges of chiral cocrystallization. KW - In situ KW - Mechanochemistry KW - XRD PY - 2018 UR - https://pubs.rsc.org/en/Content/ArticleLanding/CE/2018/C8CE01338A#!divAbstract DO - https://doi.org/10.1039/c8ce01338a SN - 1466-8033 VL - 20 IS - 45 SP - 7308 EP - 7321 PB - Royal Society of Chemistry CY - London AN - OPUS4-46913 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - New insights in mechanochemical processes using real-time in situ investigations N2 - Mechanochemistry is increasingly used for synthesizing various materials including metal organic compounds and cocrystals. Although this synthesis approach offers a fast and pure synthesis in high yields, there is a lack in understanding the mechanisms of milling reactions. The necessary data can only be obtained in in situ experiments, which were only recently established for milling reactions. Herein, we present a novel setup enabling a combined in situ investigation of mechanochemical reactions using synchrotron XRD and Raman spectroscopy. T2 - ECM31 CY - Oviedo, Spain DA - 18.08.2018 KW - Mechanochemistry KW - In situ PY - 2018 AN - OPUS4-46990 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Understanding mechanochemical reactions: Real-time insights and collaborative research N2 - Mechanochemistry emerges as a potent, environmentally friendly, and straightforward approach for crafting novel multicomponent crystal systems. Various milling parameters, including milling frequency, time, filling degree of the milling jar, ball diameter, vessel size, degree of milling ball filling, and material of jars, are recognized influencers on the mechanisms and rates of product formation. Despite the growing interest in mechanochemistry, there exists a gap in understanding the mechanistic aspects of mechanochemical reactivity and selectivity. To address this, diverse analytical methods and their combinations, such as powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography, have been developed for real-time, in situ monitoring of mechanochemical transformations. This discussion centers on our recent findings, specifically investigating the formation of (polymorphic) cocrystals and metal-organic frameworks. Through these studies, we aim to unravel the impact of milling parameters and reaction sequences on the formation mechanism and kinetics. Notably, in the mechanochemical chlorination reaction of hydantoin, normalizing kinetic profiles to the volume of the milling ball unequivocally demonstrates the conservation of milling reaction kinetics. In this ball-milling transformation, physical kinetics outweigh chemical factors in determining reaction rates. Attempting to interpret such kinetics solely through chemical terms poses a risk of misinterpretation. Our results highlight that time-resolved in situ investigations of milling reactions provide a novel avenue for fine-tuning and optimizing mechanochemical processes. T2 - PhD Seminar CY - Online meeting DA - 12.10.2023 KW - Mechanochemistry KW - In situ PY - 2023 AN - OPUS4-59022 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Investigating the mechanism and kinetics of the mechanochemical synthesis of multi-component systems N2 - Mechanochemistry is a promising and environmentally friendly approach for synthesizing (novel) multicomponent crystal systems. Various milling parameters, such as milling frequency, milling time, and ball diameter have been shown to influence the mechanisms and rates of product formation. Despite increasing interest in mechanochemistry, there is still limited understanding of the underlying reactivity and selectivity mechanisms. Various analytical techniques have been developed to gain insight into the mechanochemical transformations, including powder X-ray diffraction, X-ray adsorption spectroscopy, NMR, Raman spectroscopy and thermography. Using these techniques, we have studied the formation of (polymorphic) cocrystals, organometallic compounds and salts, and elucidated the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. For example, our study of the mechanochemical chlorination reaction of hydantoin revealed that normalisation of the kinetic profiles to the volume of the grinding ball clearly showed that physical kinetics dominate the reaction rates in a ball-milling transformation. Attempts to interpret such kinetics in purely chemical terms risk misinterpretation of the results. Our results suggest that time-resolved in situ investigation of milling reactions is a promising way to fine-tune and optimise mechanochemical processes. T2 - ISIC 2023 CY - Glasgow, Scotland DA - 05.09.2023 KW - Mechanochemistry KW - Polymorphy KW - In situ PY - 2023 AN - OPUS4-59023 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Understanding mechanochemical reactions: Real-time insights and collaborative research N2 - Mechanochemistry emerges as a potent, environmentally friendly, and straightforward approach for crafting novel multicomponent crystal systems. Various milling parameters, including milling frequency, time, filling degree of the milling jar, ball diameter, vessel size, degree of milling ball filling, and material of jars, are recognized influencers on the mechanisms and rates of product formation. Despite the growing interest in mechanochemistry, there exists a gap in understanding the mechanistic aspects of mechanochemical reactivity and selectivity. To address this, diverse analytical methods and their combinations, such as powder X-ray diffraction, X-ray absorption spectroscopy, NMR, Raman spectroscopy, and thermography, have been developed for real-time, in situ monitoring of mechanochemical transformations. This discussion centers on our recent findings, specifically investigating the formation of (polymorphic) cocrystals and metal-organic frameworks. Through these studies, we aim to unravel the impact of milling parameters and reaction sequences on the formation mechanism and kinetics. Notably, in the mechanochemical chlorination reaction of hydantoin, normalizing kinetic profiles to the volume of the milling ball unequivocally demonstrates the conservation of milling reaction kinetics. In this ball-milling transformation, physical kinetics outweigh chemical factors in determining reaction rates. Attempting to interpret such kinetics solely through chemical terms poses a risk of misinterpretation. Our results highlight that time-resolved in situ investigations of milling reactions provide a novel avenue for fine-tuning and optimizing mechanochemical processes. T2 - Brimingham Green chemistry CY - Birmingham, England DA - 08.09.2023 KW - Mechanochemistry KW - Green Chemistry PY - 2023 AN - OPUS4-59024 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Understanding mechanochemical reactions: Real-time insights and collaborative research N2 - Mechanochemistry has become a compelling method for producing (new) molecule s and mate-rials, but the inner workings of the milling jars remain a fascinating mystery. Advances in this field include tailor-made chemical systems and real-time revelations using techniques such as XRD and Raman spectroscopy. This talk will discuss our recent progress in using X-ray diffraction and sophisticated spectros-copy to observe reactions in various material systems during ball milling and extrusion in real-time. The complexity of mechanochemical reactions spans multiple scales and requires a holistic ap-proach. The categorisation of reactions by investigative methods precedes the exploration of real-time analysis that reveals macroscopic processes using synchrotron techniques. During this exploration, one resounding realisation remains: We are on the threshold of under-standing. The complexity of mechanochemistry requires a collective effort, drawing on the ex-pertise of a diverse community. As we unravel the web of mechanochemical phenomena, we acknowledge the collaborative nature of this ongoing journey. T2 - CMCC Mechanochemistry Discussions CY - Online meeting DA - 21.09.2023 KW - Mechanochemistry KW - In situ PY - 2023 AN - OPUS4-59026 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Casali, Lucia T1 - Use of the solvent-free mechanochemical method for a sustainable preparation of pharmaceuticals N2 - With the growing interest in environmental issues on the part of governments and institutions, pharmaceutical industries are asked to reduce their environmental footprint. Given the major impact related to the use of solvents, the development of methodologies less solvent demanding is nowadays even more urgent. In light of that, mechanochemistry would be a suitable solvent-free technology since it promotes the activation of the chemical reactions between (generally) solid materials via inputs of mechanical energy. Since such reactions may occur outside the kinetic and thermodynamic rules of conventional solution chemistry, the main limit of mechanochemistry is the poor mechanistic understanding of the solid-state transformations involved, which is still hindering a widespread use of the method, as well a scale-up to the industrial level. However, the development of methods for real-time monitoring of the mechanochemical reactions enables obtaining (in)accessible information on reaction intermediates, new products, or reaction time, thus getting closer to a better understanding of the mechanistic behaviour. With the rules of this chemistry becoming increasingly clear, the new reaction pathways of mechanochemistry wouldn’t represent a limit anymore, but an asset, that may lead to lot of opportunities for the pharmaceutical industry. T2 - Post Doc Day Berlin CY - Berlin, Germany DA - 02.11.2023 KW - Mechanochemistry KW - Sustainability KW - Pharmaceuticals PY - 2023 AN - OPUS4-59010 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - de Olivera, Paulo A1 - Michalchuk, Adam A1 - Marquardt, Julien A1 - Feiler, Torvid A1 - Prinz, Carsten A1 - Torresi, R. A1 - Camargo, P. A1 - Emmerling, Franziska T1 - Investigating the role of reducing agents on mechanosynthesis of Au nanoparticles N2 - Control over the bottom up synthesis of metal nanoparticles (NP) depends on many experimental factors, including the choice of stabilising and reducing agents. By selectively manipulating these species, it is possible to control NP characteristics through solution-phase synthesis strategies. It is not known, however, whether NPs produced from mechanochemical syntheses are governed by the same rules. Using the Au NPs mechanosynthesis as a model system, we investigate how a series of common reducing agents affect both the reduction kinetics and size of Au NPs. It is shown that the relative effects of reducing agents on mechanochemical NP synthesis differ significantly from their role in analogous solution-phase reactions. Hence, strategies developed for control over NP growth in solution are not directly transferrable to environmentally benign mechanochemical approaches. This work demonstrates a clear need for dedicated, systematic studies on NP mechanosynthesis. KW - Mechanochemistry KW - Metal nanoparicels PY - 2020 DO - https://doi.org/10.1039/d0ce00826e VL - 22 IS - 38 SP - 6261 EP - 6267 PB - Royal Society of Chemistry AN - OPUS4-51757 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kulla, Hannes A1 - Haferkamp, Sebastian A1 - Akhmetova, Irina A1 - Röllig, Mathias A1 - Maierhofer, Christiane A1 - Rademann, Klaus A1 - Emmerling, Franziska T1 - In situ investigations of mechanochemical one-pot syntheses N2 - We present an in situ triple coupling of synchrotron X-ray diffraction with Raman spectroscopy, and thermography to study milling reactions in real time. This combination of methods allows a correlation of the structural evolution with temperature information. The temperature information is crucial for understanding both the thermodynamics and reaction kinetics. The reaction mechanisms of three prototypical mechanochemical syntheses, a cocrystal formation, a C@C bond formation (Knoevenagel condensation), and the formation of a manganese-phosphonate, were elucidated. Trends in the temperature development during milling are identified. The heat of reaction and latent heat of crystallization of the product contribute to the overall temperature increase. A decrease in temperature occurs via release of, for example, water as a byproduct. Solid and liquid intermediates are detected. The influence of the mechanical impact could be separated from temperature effects caused by the reaction. KW - In situ studies KW - Mechanochemistry KW - Raman spectroscopy KW - Thermography KW - X-ray diffraction PY - 2018 DO - https://doi.org/10.1002/anie.201800147 SN - 1433-7851 SN - 1521-3773 VL - 57 IS - 20 SP - 5930 EP - 5933 PB - Wiley-VCH CY - Weinheim AN - OPUS4-44946 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Haferkamp, Sebastian A1 - Emmerling, Franziska T1 - Insights into the mechanochemical Knoevenagel condensation N2 - Mechanochemistry paves the way to simple, fast, and green syntheses, but there is a lack in understanding of the underlying mechanisms. Here, we present a universal strategy for simultaneous real-time in situ analysis, combining X-ray diffraction, Raman spectroscopy, and thermography. T2 - Bessy User Meeting 2019 CY - Berlin, Germany DA - 05.12.2019 KW - Mechanochemistry PY - 2019 AN - OPUS4-50122 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - May, Anastasia T1 - Thermomechanochemical Synthesis of Pimelic Acid Cocrystals N2 - Milling temperature is a critical factor in mechanochemistry, affecting the kinetics and outcomes of reactions. In the context of cocrystallization, the influence of milling temperature on the process has been investigated for cocrystal systems pyrazinamide:pimelic acid (PZA:PA) and 4,4'-bipyridine:pimelic acid (BPY:PA). By means of temperature-controlled milling, stabilization of metastable polymorph of PZA:PA was achieved, thereby decelerating the aging process of the polymorph. This was accomplished through controlled heated milling of PZA and PA. Furthermore, we have successfully synthesized all three BPY:PA polymorphs by mechanochemistry involving controlled cooled and heated milling. In previous studies, only the most stable polymorph was obtained by mechanochemistry. T2 - 10th European Crystallography School CY - Ohrid, North Macedonia DA - 23.06.2025 KW - Mechanochemistry KW - Cocrystal PY - 2025 AN - OPUS4-63797 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - Strontium-coordination polymers based on tetrafluorophthalic and phthalic acids: mechanochemical synthesis, ab initio structures determination, and spectroscopic characterization N2 - Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible. KW - Mechanochemistry KW - XRD KW - NMR PY - 2017 DO - https://doi.org/10.1039/c7dt02564e SN - 1477-9226 SN - 1477-9234 VL - 46 IS - 37 SP - 12574 EP - 12587 PB - The Royal Society of Chemistry CY - Cambridge AN - OPUS4-42261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gugin, Nikita A1 - Villajos Collado, José Antonio A1 - Dautain, O. A1 - Maiwald, Michael A1 - Emmerling, Franziska T1 - Optimizing the Green Synthesis of ZIF-8 by Reactive Extrusion Using In Situ Raman Spectroscopy N2 - We report the scale-up of a batch solid synthesis of zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in the extruder directly under the mixture of solid 2-methylimidazole and basic zinc carbonate in the presence of a catalytic amount of liquid. The process parameters such as temperature, liquid type, feeding rate, and linker excess were optimized using the setup specifically designed for in situ Raman spectroscopy. Highly crystalline ZIF-8 with a Brunauer–Emmett–Teller (BET) surface area of 1816 m2 g–1 was quantitatively prepared at mild temperature using a catalytic amount of ethanol and a small excess of the linker. Finally, we developed a simple and comprehensive approach to evaluating the environmental friendliness and scalability of metal–organic framework (MOF) syntheses in view of their large-scale production. KW - Mechanochemistry KW - In situ Raman KW - Large-scale processing KW - Metal−organic frameworks KW - Twin-screw extrusion (TSE) PY - 2023 DO - https://doi.org/10.1021/acssuschemeng.2c07509 SN - 2168-0485 VL - 11 IS - 13 SP - 5175 EP - 5183 PB - ACS Publications AN - OPUS4-57366 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Moss, Caitlin T1 - Mechanochemistry as a Green Synthetic Route N2 - Mechanochemistry has emerged as a transformative approach in sustainable chemistry, offering a solvent-free and energy-efficient pathway for chemical synthesis. By utilizing mechanical force—typically through ball milling, grinding, or other shear-driven methods, reactions can proceed without the extensive use of harmful solvents, reducing waste and environmental impact. This poster explores the principles, methodologies, and applications of mechanochemistry in developing greener synthetic routes, with a focus on pharmaceutical and materials science applications. Key advantages, including reduced reaction times, enhanced selectivity, and improved atom economy, will be highlighted alongside challenges such as scalability. By presenting mechanochemistry as a frontier technology at the intersection of chemistry, materials science, and environmental stewardship, this work invites dialogue among students and academics about its future in sustainable innovation. T2 - Furture WINS 2024 CY - Berlin, Germany DA - 21.11.2024 KW - Mechanochemistry KW - Green chemistry PY - 2024 AN - OPUS4-62123 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Emmerling, Franziska T1 - Mechanochemical Syntheses of Metal Phosphonates N2 - Mechanochemistry is a suitable method for synthesizing a variety of metal phosphonates. By varying the ratio of the reactants, it is possible to control the reaction pathway. With this approach targeted synthesis of a certain composition is possible. Several new metal phosphonate structures were solved from the powder X-ray diffraction data including molecular metal phosphonates. The results demonstrate a new fast, facile, and environmental friendly alternative for the preparation of metal phosphonates. In situ investigations of the milling processes provided insights into the formation process of metal phosphonates. A multi-step diffusion mechanism was identified for most systems. Crystalline phases were obtained intermediately, suggesting that the synthesis is following Ostwald’s rules of stages. T2 - 1st European Workshop on Metalphophantes CY - Swanse, UK DA - 18.09.2018 KW - Mechanochemistry PY - 2018 AN - OPUS4-46382 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Haferkamp, Sebastian T1 - Mechanochemical Knoevenagel condensations of benzaldehyde derivates investigated in situ N2 - Mechanochemistry is widely applicable for the synthesis of inorganic, metal-organic, and organic compounds. It is known for short reaction times, nearly quantitative conversions, and decreasing amount of solvents, which opens the field to more environmentally friendly syntheses routes. Among organic syntheses, the Knoevenagel condensation is an important C-C bond forming reaction leading to α,β-unsaturated compounds. To gain more information on the underlying processes, we investigated the syntheses by a combination of different in situ investigation techniques, including synchrotron X-ray diffraction, Raman spectroscopy and thermography. This combination provides information on the structural changes and temperature influences during milling. Benzaldehyde derivates (nitro- and fluoro-derivates) reacted with malononitrile to the respective benzylidenemalononitriles. The in situ investigations show direct and quantitative conversions. In the case of the fluorinated benzaldehyde derivates we showed the possibility of using liquid substrates in mechanochemical organic synthesis. Surprisingly, after crystallization from a viscous state, the material was suitable for single-crystal X-ray analysis. T2 - Powder Diffraction School 2018 CY - Villigen, Switzerland DA - 24.09.2018 KW - C-C coupling KW - Mechanochemistry KW - In situ KW - Knoevenagel PY - 2018 AN - OPUS4-46320 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kulla, Hannes T1 - In situ investigations of a mechanochemical cocrystal formation by X-ray diffraction in two different milling jars N2 - We present an in situ PXRD investigation of the mechanochemical cocrystal formation of pyrazinamide with pimelic acid in two milling jar materials. DFT calculations of the two synthesized polymorphs suggest that the relative stability is based on a conformation change of pyrazinamide in the cocrystal. T2 - 3. BAM-BfR Workshop CY - Berlin, Adlershof, Germany DA - 15.02.2018 KW - Mechanochemistry KW - Cocrystal KW - Polymorph KW - In situ XRD KW - DFT PY - 2018 AN - OPUS4-44315 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Casali, Lucia T1 - Kinetics of the mechanically induced ibuprofen-nicotinamide co-crystal formation by in-situ X-ray diffraction N2 - Mechanochemistry offers sustainable synthesis for pharmaceuticals, though scaling remains challenging. By combining time-resolved in situ X-ray diffraction with kinetic modeling on the mechanosynthesis of the co-crystal ibuprofen-nicotinamide, we identified the reaction-driving factors. This deeper insight opens the way for a scale-up of mechanochemistry in the pharmaceutical industry. T2 - CGOM15 (15th International Workshop on Crystal Growth of Organic Materials) CY - Phuket, Thailand DA - 23.07.2024 KW - Mechanochemistry KW - Kinetics KW - In-situ monitoring PY - 2024 AN - OPUS4-61756 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Casali, Lucia T1 - Kinetics of the mechanically induced ibuprofen-nicotinamide co-crystal formation by in-situ X-ray diffraction N2 - Mechanochemistry offers sustainable synthesis for pharmaceuticals, though scaling remains challenging. By combining time-resolved in situ X-ray diffraction with kinetic modeling on the mechanosynthesis of the co-crystal ibuprofen-nicotinamide, we identified the reaction-driving factors. This deeper insight opens the way for a scale-up of mechanochemistry in the pharmaceutical industry. T2 - BESSY User meeting CY - Berlin, Germany DA - 11.12.2024 KW - Mechanochemistry KW - Kinetics KW - In-situ monitoring PY - 2024 AN - OPUS4-62193 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -