TY - CONF A1 - Stolar, Tomislav T1 - Mechanochemical conversion of polyethylene terephthalate into valuable metal-organic frameworks N2 - Single-use plastics are causing plastic pollution, and less than 10% of plastic waste is recycled globally. Here, we present a sustainable mechanochemical1 protocol for converting post-consumer polyethylene terephthalate (PET) textile and bottles into the porous metal-organic framework (MOF) UiO-66. We used time-resolved in situ synchrotron powder X-ray diffraction and Raman spectroscopy to monitor the depolymerization of PET during ball milling with sodium and potassium hydroxide and water as a liquid additive (Figure 1). For synthesizing UiO-66, we focused on the better performing sodium hydroxide and optimized two distinct synthetic routes to produce high-quality UiO-66. Our results demonstrate the potential of mechanochemistry to enable more circular MOF synthesis using post-consumer PET waste. T2 - The International Symposium on Mechanochemistry (Mech’cheM) 2025: New forces in Mechanochemistry CY - Montpellier, France DA - 04.06.2025 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2025 AN - OPUS4-63943 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Sustainable mechanochemical reaction engineering: from molecular mechanisms to scalable technology N2 - In this talk, I will present about our quest to fundamentally understand mechanochemical reactions by in situ monitoring studies. Another of our interest is scaling up mechanochemistry. For example, we are now working on developing mechanochemical technology to enable a circular economy of plastics. T2 - Korea-Germany Symposium on Mechanochemistry CY - Jeonju, South Korea DA - 02.10.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62110 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Mechanochemistry: fundamentals to application N2 - In the first part, I will talk about the role of mechanochemistry in prebiotic chemistry. For example, prebiotically plausible pathways to peptides from inactivated amino acids are unclear as most oligomerization approaches rely on thermodynamically disfavored reactions in solution. I will show how a combination of mineral surfaces and mechanochemical activation enables the oligomerization of amino acids to oligopeptides (Figure 1). In the second part, I will show how fundamental studies inspired to use mechanochemistry for the sustainable synthesis of commercially relevant compounds, in line with the United Nations Sustainable Development Goals.2 We developed a solvent-free thermo-mechanochemical approach for the direct coupling of carboxylic acids and amines, which avoids activators and additives. We applied our methodology for the quantitative synthesis of the active pharmaceutical ingredient moclobemide (Figure 2). T2 - Solutions in Chemistry Conference 2024 CY - Sveti Martin na Muri, Croatia DA - 15.11.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62111 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Sustainable mechanochemical reaction engineering: from molecular mechanisms to scalable technology N2 - In this talk, I will present about our quest to fundamentally understand mechanochemical reactions by in situ monitoring studies. Another of our interest is scaling up mechanochemistry. For example, we are now working on developing mechanochemical technology to enable a circular economy of plastics. T2 - Hokkaido International Workshop on Mechanochemistry CY - Hokkaido, Japan DA - 29.09.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62109 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Upcycling waste PET bottles to porous UiO-66 by mechanochemistry N2 - Single-use plastics are causing plastic pollution, and less than 10% of plastic waste gets recycled globally. Most of it ends up in landfills or gets incinerated in a highly unsustainable manner. Here, I will present a sustainable mechanochemical protocol for the chemical upcycling of polyethylene terephthalate (PET) to porous UiO-66 metal-organic framework (MOF). In the first step, PET is ball-milled with sodium hydroxide and undergoes alkaline hydrolysis to disodium terephthalate (Na2TP). Time-resolved in situ monitoring of ball milling reaction by synchrotron powder X-ray diffraction shows the appearance of crystalline Na2TP after 20 min of milling. However, ex-situ analysis at different milling times by gel permeation chromatography reveals that the depolymerisation step needs more milling for completion. After two hours of ball milling, there are only trace amounts of leftover PET. For upcycling to UiO-66, a zirconium acetate cluster is added to Na2TP together with liquid additives and after milling for T2 - International Conference on Resource Chemistry 2024 CY - Alzenau, Germany DA - 13.03.2024 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2024 AN - OPUS4-62105 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 - Gugin, Nikita T1 - Large-scale green synthesis of a model bsa@zif-8 biocomposite via reactive extrusion N2 - Metal-organic framework-based biocomposites (MOF-biocomposites) hold significant promise for applications in biosensing, biocatalysis, and delivery of biopharmaceuticals. One of the most studied MOFs for bioapplications is ZIF-8 (zeolitic imidazolate framework 8) due to its high surface area, high thermal and chemical stability, and low cytotoxicity. The conventional synthesis method for ZIF-8-biocomposites, known as biomimetic mineralization, involves mixing specific biomolecules, 2-methylimidazole, and a soluble Zn2+ source in water. While this method is highly efficient, it has limitations in terms of scalability and is restricted to hydrophilic biomolecules. Aimed at developing a scalable and versatile approach, we adapted our recently reported ZIF-8 reactive extrusion for biocomposite production. For the preparation of biocomposites, bovine serum albumin (BSA) was selected as an inexpensive model biomacromolecule. The synthesis of BSA@ZIF-8 was carried out using a twin-screw extruder at a mild temperature of 40 °C, employing a catalytic amount of EtOH following our previously explored procedure[4]. Comprehensive characterization using powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FTIR, N2 adsorption, confocal laser scanning microscopy (CLSM), and Bradford assay allowed us to optimize reaction conditions and quantify the amount of encapsulated BSA. After thoroughly washing the extrudate with ethanol to eliminate surface-adsorbed BSA molecules, we obtained highly crystalline and pure BSA@ZIF-8 with varying BSA loadings. Notably, achieving a maximum BSA encapsulation of 26wt% was possible with 40wt% BSA in the reagent mixture. With 5wt% BSA, we reached a high encapsulation efficiency of 96%, a critical aspect for the cost-effective production of biocomposites involving expensive biomolecules. A continuous extruder operation under optimized conditions demonstrated consistent product quality, enabling the production of biocomposites on a 1.2 kd d-1 scale with a space-time yield of approximately 30000 kg m−3 d−1. These findings offer valuable insights into the cost-effective and large-scale production of ZIF-8-based biocomposites. Moreover, due to its solid-state nature, this reaction is independent of the hydrophilic or hydrophobic properties of biomolecules, providing flexibility and advantages over solvent-based processes. T2 - International Conference on Resource Chemistry 2024 CY - Alzenau, Germany DA - 12.03.2024 KW - Reactive Extrusion KW - Mechanochemistry PY - 2024 AN - OPUS4-61399 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Gugin, Nikita T1 - Mechanochemistry: the Art of Upscaling N2 - "Mechanochemistry: The Art of Upscaling" talk explores the transition from small-scale ball milling reactions to large-scale production using reactive extrusion. This talk focuses on the challenges and strategies involved in scaling up mechanochemical processes, emphasizing the critical role of in situ monitoring techniques such as Raman spectroscopy and energy-dispersive X-ray diffraction (EDXRD). These methods provide real-time insights into reaction dynamics and phase changes, enabling the optimization of process parameters for efficient and controlled upscaling. The discussion highlights key advancements in the field and their industrial applications. T2 - SALSA Make and Measure conference CY - Berlin, Germany DA - 11.09.2024 KW - Mechanochemistry KW - Reactive extrusion PY - 2024 AN - OPUS4-61397 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Thermo mechanochemistry: merging heat and force for discovering new chemical transformations N2 - Mechanochemistry is a hot topic in chemistry, and the number of researchers from academia and industry joining the field is growing. Mechanical action drives chemical reactions forward independently of the solubility of reactants and drastically minimises solvent usage and waste production. Mechanochemistry also provides other advantages, such as faster reaction times, higher yields, altered selectivity, and access to products not obtainable by other methods. Furthermore, recent innovations in mechanochemistry enable conducting chemical reactions by combining force and heat in approach called thermo-mechanochemistry [1]. These conditions typically overcome high activation energies and access products not obtainable by mechanochemistry at ambient temperature conditions. In this talk, I will give an overview to this emerging topic and to our discoveries by thermo-mechanochemistry that include prebiotic peptide bond formation [2], synthesis of amide-based active pharmaceutical ingredient [3], condensation of diamondoid derivatives [4], and manipulation of polymorphic transition temperatures in organic molecular crystals [5]. T2 - Department Seminar at Newcastle University CY - Newcastle, UK DA - 15.09.2023 KW - Mechanochemistry PY - 2023 AN - OPUS4-62104 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Stolar, Tomislav T1 - Grinding away plastic waste: enabling the circular economy of plastics N2 - Single-use plastics are causing plastic pollution, and less than 10% of plastic waste gets recycled globally. Most of it ends up in landfills or is being incinerated in a highly unsustainable manner. Plastic waste in the environment endangers ecosystems, and microplastics in babies raise alarming health concerns. Hence, one of the global priorities is circular economy for plastics which does not further exploit fossil fuel feedstocks. However, current technologies like mechanical recycling are inadequate, and innovative ones such as chemical recycling, i.e., converting plastics back to the starting monomers, are essential. For example, we can use the recycled monomers to make new plastics in a circular manner or upcycle them to other value-added functional materials. Here, I will present a sustainable technology we developed for the chemical recycling of polyethylene terephthalate (PET). PET represents 10% of global plastic production and dominates in plastic packaging. The technology relies on mechanochemistry (grinding) which uses mechanical action for the chemical breakdown of plastic polymers in an environmentally friendly way. The next step in our research is to use life cycle and techno-economic assessment to validate the sustainability and commercial viability of our technology with the goal of transferring it to real-world industrial application. T2 - Berlin PostDoc Day 2023 CY - Berlin, Germany DA - 02.11.2023 KW - Mechanochemistry KW - Plastic recycling KW - Circular economy PY - 2023 AN - OPUS4-62103 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -