TY - CONF
A1 - Akhmetova, Irina
T1 - Mechanochemical synthesis of metal phosphonates
N2 - The exploration of metal phosphonates chemistry has gained great interest during the last decades, because of their structural diversity. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reactions (OER).
Here, we present the in situ investigation of mechanochemical syntheses of different manganese phosphonates by synchrotron X-ray diffraction. Nitrilotri(methylenephosphonic acid) and N,N-Bis(phosphonomethyl)glycine were chosen as ligands. The liquid-assisted milling process can be divided into three steps, including an amorphous stage. One of the products has not been obtained by classical solution chemistry before.
These metal phosphonates and/or their derivatives are considered to be active in electrochemical energy conversion. The verification of their applicability is one of the topics of our resent research.
T2 - Fundamental Bases of Mechanochemical Technologies
CY - Novosibirsk, Russia
DA - 25.06.2018
KW - Metal phosphonates
KW - Mechanochemistry
KW - PXRD
KW - Thermography
PY - 2018
AN - OPUS4-46996
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Akhmetova, Irina
T1 - In situ investigation of milling reactions and structure determination of the products using X-ray diffraction
N2 - Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. By milling the reactants, various organic, inorganic, and metal-organic compounds can be obtained in high yields. Although mechanochemistry is widely used, the underlying mechanisms are not fully understood making mechanochemical reactions difficult to predict. Metal phosphonates are metal-organic compounds accessible by grinding. Because of their structural diversity, the exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reaction (OER). Here, we present the in situ investigation of the mechanochemical synthesis of a manganese(II)-phosphonate by synchrotron X-ray diffraction and thermography. The product has not been obtained by classical solution chemistry before and its crystal structure was determined from PXRD data. The milling process can be divided into different steps, with the product crystallization corresponding with the highest temperature rise. The activity of this metal phosphonate towards OER was measured and is presented here.
T2 - International School of Crystallography - 52nd Course: Quantum Crystallography
CY - Erice, Italy
DA - 1.06.2018
KW - Metal phosphonates
KW - Mechanochemistry
KW - PXRD
KW - OER
KW - Thermography
PY - 2018
AN - OPUS4-46998
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Akhmetova, Irina
T1 - In situ investigation of mechanochemical syntheses of metal phosphonates
N2 - We report on the in situ investigation of mechanochemical syntheses of metal phosphonates. The metal phosphonates are formed in milling reactions starting from a metal acetate and a phosphonic acid. The conversions are observed by synchrotron PXRD and Raman spectroscopy to shed light on the reaction mechanisms including possible intermediates.
T2 - 8th HZB User Meeting
CY - Berlin, Germany
DA - 07.12.2016
KW - Mechanochemistry
KW - In situ
KW - Metal phosphonates
KW - XRD
KW - Raman spectroscopy
PY - 2016
AN - OPUS4-38780
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Akhmetova, Irina
T1 - In situ investigation of mechanochemical syntheses of manganese phosphonates with N-containing ligands
N2 - Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. The exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades due to their structural diversity. We synthesized manganese phosphonates in milling reactions. The mechanochemical reactions were investigated in situ to reveal the underlying mechanisms.
T2 - Joint BER II and BESSY II User Meeting
CY - Berlin, Germany
DA - 05.12.2018
KW - Metal phosphonates
KW - Mechanochemistry
KW - PXRD
KW - In situ
KW - Thermography
PY - 2018
AN - OPUS4-46999
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Akhmetova, Irina
A1 - Schuzjajew, K.
A1 - Wilke, M.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Rademann, K.
A1 - Roth, C.
A1 - Emmerling, Franziska
T1 - Synthesis, characterization and in situ monitoring of the mechanochemical reaction process of two manganese(II)-phosphonates with N-containing ligands
N2 - Two divalent manganese aminophosphonates, manganese mono (nitrilotrimethylphosphonate) (MnNP3) and manganese bis N-(carboxymethyl)iminodi(methylphosphonate)) (Mn(NP2AH)2), have been prepared by mechanochemical synthesis and characterized by powder X-ray diffraction (PXRD). The structure of the novel compound Mn(NP2AH)2 was determined from PXRD data. MnNP3 as well as Mn(NP2AH)2 exhibits a chain-like structure.
In both cases, the manganese atom is coordinated by six oxygen atoms in a distorted octahedron. The local coordination around Mn was further characterized by extended X-ray absorption fine structure. The synthesis process was followed in situ by synchrotron X-ray diffraction revealing a three-step reaction mechanism. The asprepared manganese(II) phosphonates were calcined on air.
All samples were successfully tested for their suitability as catalyst material in the oxygen evolution reaction.
KW - Mechanochemistry
KW - In situ
KW - XRD
PY - 2018
DO - https://doi.org/10.1007/s10853-018-2608-6
SN - 0022-2461
SN - 1573-4803
VL - 53
IS - 19
SP - 13390
EP - 13399
PB - Springer Science + Business Media B.V.
AN - OPUS4-45673
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 - JOUR
A1 - Al-Terkawi, Abdal-Azim
A1 - Scholz, G.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinsch, Stefan
A1 - Kemnitz, E.
A1 - Emmerling, Franziska
T1 - Ca- and Sr- tetrafluoroisophthalates: mechanochemical synthesis, characterization, and ab initio structure determination
N2 - New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials.
KW - Mechanochemistry
KW - In situ
KW - XRD
KW - Coordination polymers
PY - 2017
UR - http://pubs.rsc.org/-/content/articlehtml/2017/dt/c7dt00734e
DO - https://doi.org/10.1039/c7dt00734e
VL - 46
IS - 18
SP - 6003
EP - 6012
AN - OPUS4-41516
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 - Mechanochemical synthesis, characterization, and structure determination of new alkaline earth metal-tetrafluoroterephthalate frameworks: Ca(pBDC‑F4 )·4H2O, Sr(pBDC‑F4 )·4H2O, and Ba(pBDC‑F4 )
N2 - New fluorinated alkaline earth metal−organic frameworks were successfully synthesized by milling of metal hydroxides M(OH)2 with tetrafluoroterephthalic acid H2 pBDC-F4. Both calcium- and strontium-tetrafluoroterephthalates are tetrahydrated, while the barium tetrafluoroterephthalate is free of coordinating water molecules. The two isomorphic structures Ca(pBDC-F4)·4H2O and Sr(pBDC-F4)·4H2O were solved from the powder diffraction data by ab initio structure determination and subsequent Rietveld refinement. The products were thoroughly characterized by elemental analysis, thermal analysis, magicangle spinning NMR, Fourier transform infrared spectroscopy, scanning electron microscopy imaging, and Brunauer−Emmett−Teller measurements. Our findings suggest that the mechanochemical synthesis route is a promising approach for the preparation of new fluorinated alkaline earth metal−organic frameworks.
KW - Mechanochemistry
KW - MOFs
KW - XRD
PY - 2016
UR - http://pubs.acs.org/doi/abs/10.1021/acs.cgd.5b01457
DO - https://doi.org/10.1021/acs.cgd.5b01457
SN - 1528-7483
VL - 16/4
SP - 1923
EP - 1933
PB - American Chemical Society
CY - Washington, DC, USA
AN - OPUS4-35940
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 - Al-Terkawi, Abdal-Azim
A1 - Scholz, G.
A1 - Prinz, Carsten
A1 - Zimathies, Annett
A1 - Emmerling, Franziska
A1 - Kemnitz, E.
T1 - Hydrated and dehydrated Ca-coordination polymers based on benzene-dicarboxylates: mechanochemical synthesis, structure refinement, and spectroscopic characterization
N2 - A series of Ca-based coordination polymers were prepared mechanochemically by milling Ca(OH)2 with phthalic acid (H2oBDC), isophthalic acid (H2mBDC), and terephthalic acid (H2pBDC). The hydrated compounds [Ca(oBDC)(H2O)], [Ca(mBDC)(H2O)3.4], and [Ca(pBDC)(H2O)3] were prepared for the first time via mechanochemical routes. The refined structures were validated by extended X-ray absorption data. The new dehydrated compound [Ca(oBDC)] (1-H2O), obtained after the thermal post-treatment of 1 in a reversible phase transition process, was determined ab initio based on the powder X-ray diffraction (PXRD) data. The materials were thoroughly characterized using elemental analysis, thermal analysis, and spectroscopic methods: magic-angle spinning NMR and attenuated total reflection-infrared spectroscopy. The specific surface areas and sorption properties of the hydrated and dehydrated samples were determined using the isotherms of gas sorption and dynamic vapor sorption measurements.
KW - Mechanochemistry
KW - XRD
PY - 2018
UR - http://pubs.rsc.org/en/content/articlehtml/2017/ce/c7ce01906h
DO - https://doi.org/10.1039/C7CE01906H
VL - 20
SP - 946
EP - 961
PB - Royal Society of Chemistry
AN - OPUS4-44440
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Alić, Jasna
A1 - Schlegel, Moritz-Caspar
A1 - Emmerling, Franziska
A1 - Stolar, Tomislav
T1 - Meeting the UN Sustainable Development Goals with Mechanochemistry
N2 - Chemistry traditionally relies on reactions in solution, but this method is increasingly problematic due to the scale of chemical processes and their economic and environmental impact. Handling residual chemical waste, including solvents, incurs significant costs and environmental pressure. Conversely, novel chemical approaches are needed to address pressing societal issues such as climate change, energy scarcity, food insecurity, and waste pollution. Mechanochemistry, a sustainable chemistry discipline that uses mechanical action to induce chemical reactivity without bulk solvents, is a hot topic in academic research on sustainable and green chemistry. Given its fundamentally different working principles from solution chemistry, mechanochemistry offers more efficient chemical processes and the opportunity to design new chemical reactions. Mechanochemistry has a profound impact on many urgent issues facing our society and it is now necessary to use mechanochemistry to address them. This Minireview aims to provide a guide for using mechanochemistry to meet the United Nations (UN) Sustainable Development Goals (SDGs), thereby contributing to a prosperous society. Detailed analysis shows that mechanochemistry connects with most UN SDGs and offers more cost‐efficiency than other approaches together with a superior environmental performance.
KW - Mechanochemistry
KW - SDGs
PY - 2024
DO - https://doi.org/10.1002/anie.202414745
SP - 1
EP - 3
PB - Wiley
AN - OPUS4-61108
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Alić Stolar, Jasna
T1 - Harnessing mechanochemistry to combat PFAS contamination
N2 - For over 70 years, the uncontrolled production, use, and disposal of per- and polyfluoroalkyl substances (PFAS) have led to widespread global contamination, necessitating the rapid development of innovative and efficient remediation technologies. State-of-the-art strategies rely on energy-intensive incineration, which releases greenhouse gases and smaller, volatile PFAS derivatives. Here, we present a fast, simple, and sustainable method for the complete degradation of PFAS leveraging mechanochemistry to break down the persistent carbon-fluorine bonds. Our findings indicate that liquid-assisted grinding conditions accelerate the degradation of perfluorooctanoic acid compared to neat grinding conditions, resulting in a significant reduction in energy consumption. Moreover, the fluoride released during the process binds to inorganic additives, allowing fluorine recovery as crystalline salts and preventing the formation of secondary toxic waste. The method has strong potential for scaling up and offers a green and viable solution for real-world application in PFAS decontamination.
T2 - The International Symposium on Mechanochemistry (Mech’cheM 2025)
CY - Montpellier, France
DA - 04.06.2025
KW - Mechanochemistry
KW - PFAS
PY - 2025
AN - OPUS4-63956
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Alić Stolar, Jasna
T1 - Harnessing mechanochemistry to tackle PFAS pollution
N2 - We are currently facing one of the most serious environmental crises in human history – the widespread pollution caused by PFAS. PFAS stands for per- and polyfluoroalkyl substances, which are toxic, persistent, highly mobile, and bioaccumulative compounds, often referred to as 'forever chemicals'. For over 70 years, they have been used to make products resistant to water, heat, and stains, but the cost of damaging ecosystems and harming human health was revealed far too late. As of 2023, there were more than 23,000 confirmed PFAS contamination sites in Europe alone, with at least an equal number of presumptive contamination sites due to historical and current industrial activities.1 Public concern has pushed regulatory bodies to restrict the production of the most common PFAS, but with over 10,000 PFAS compounds and existing contamination, the problem remains largely unresolved.
State-of-the-art remediation strategies rely on energy-intensive incineration, which releases greenhouse gases and smaller, volatile PFAS derivatives.2 Here, we present a fast, simple, and sustainable method for the complete degradation of PFAS, leveraging mechanochemistry3 to break down the persistent carbon-fluorine bonds. Our findings indicate that liquid-assisted grinding conditions accelerate the degradation of perfluorooctanoic acid compared to neat grinding conditions, resulting in a significant reduction in energy consumption. Moreover, the fluoride released during the process binds to inorganic additives, allowing fluorine recovery as crystalline salts and preventing the formation of secondary toxic waste. The method has strong potential for scaling up and offers a green and viable solution for real-world application in PFAS decontamination.
T2 - Tag der Chemie
CY - Berlin, Germany
DA - 03.07.2025
KW - Mechanochemistry
KW - Forever chemicals
KW - Sustainability
PY - 2025
AN - OPUS4-63972
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bach, S.
A1 - Visnow, E.
A1 - Panthöfer, M.
A1 - Gorelik, T.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Gulo, A.
A1 - Kolb, U.
A1 - Emmerling, Franziska
A1 - Lind, C.
A1 - Tremel, W.
T1 - Hydrate networks under mechanical stress – A case study for Co3(PO4)2·8H2O
N2 - The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure.
The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-bonded network and the concomitant crystalline–amorphous transformation. UV/Vis spectroscopy, extended X-ray absorption spectroscopy (EXAFS), and X-ray absorption near-edge spectroscopy (XANES) provided information about the short-range order in the amorphous solid, and thermal analysis revealed its composition and showed that the moderate charge densities of the Co²⁺ and PO₄³⁻ ions, which make the hydration enthalpy comparable to the binding energy of the counteranions, and the Formation of hydrogen-bonded networks favor multistage crystallization processes associated with the release and uptake of coordinated water. The changes of the Co²⁺ coordination induce a color change from pink to blue; therefore, Co₃(PO₄)₂·8H₂O can be used as an overheat temperature indicator.
KW - Mechanochemistry
KW - Amorphous materials
KW - Hydrates
KW - Cobalt
KW - Phosphates
PY - 2016
DO - https://doi.org/10.1002/ejic.201501481
SN - 1434-1948
SN - 1099-0682
VL - 2016
IS - 13-14
SP - 2072
EP - 2081
PB - Wiley-VCH Verlag GmbH & Co. KGaA
CY - Weinheim, Germany
AN - OPUS4-36434
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Baláž, Matej
A1 - Birinci, Mustafa
A1 - Şentürk, Kader
A1 - Achimovičová, Marcela
A1 - Baláž, Peter
A1 - Tampubolon, Imelda Octa
A1 - Stolar, Tomislav
A1 - Bienert, Ralf
A1 - Emmerling, Franziska
A1 - Erdemoğlu, Sema
A1 - Sis, Hikmet
A1 - Erdemoğlu, Murat
T1 - Utilizing Taguchi method and in situ X-ray powder diffraction monitoring to determine the influence of mechanical activation conditions on the physico-chemical properties and Al leachability of K-feldspar
N2 - K-feldspar represents an important natural resource of potassium and aluminum. Within the framework of this study, the K-feldspar was mechanically activated in a planetary ball mill under different conditions planned according to 43 Taguchi orthogonal array experimental design. As outputs, specific surface area (SBET), median particle size (d50), amorphization degree of mineral phases , and Al recovery were used. It was found that the initial d50 value of 293 μm could be reduced to 6.7 μm and the SBET value of 4.7 m2/g could be increased up to 32.5 m2/g upon milling. Both microcline KAl3SiO8, and albite NaAl3SiO8 could be almost completely amorphized, whereas quartz SiO2 still maintained some crystallinity even under the most intensive conditions. Increasing SBET and decreasing the d50 values did not lead to a significant improvement in Al leach recovery, whereas a clear relationship between the amorphization of microcline and the recovered aluminum was found. Analysis of Variance (ANOVA) showed that increasing ball-to-powder ratio is the most beneficial for the improvement in Al recovery. In situ powder X-ray diffraction monitoring performed in an oscillation ball mill under synchrotron irradiation has shown very rapid amorphization of microcline phase at the beginning. However, amorphization of microcline was only partial after two hours of the treatment in this mill, apart from almost complete process in the planetary ball mill. In the end, regressions for the calculation of Al recovery by knowing the values of input parameters were calculated. In general, by just using mechanical activation without the subsequent roasting process that is commonly used to boost metal recoveries, it was possible to quantitatively recover aluminum from K-feldspar.
KW - Mechanochemistry
KW - Mechanical activation
KW - Design of experiments
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-611059
DO - https://doi.org/10.1016/j.jmrt.2024.08.156
SN - 2238-7854
VL - 32
SP - 3886
EP - 3895
PB - Elsevier B.V.
AN - OPUS4-61105
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Batteas, James
A1 - Blank, Kerstin G.
A1 - Colacino, Evelina
A1 - Emmerling, Franziska
A1 - Friščić, Tomislav
A1 - Mack, James
A1 - Moore, Jeffrey
A1 - Rivas, Maria Elena
A1 - Tysoe, Wilfred
T1 - Moving mechanochemistry forward
N2 - Arguably mechanochemistry is one of the oldest, and at the same time one of the newest, areas of chemistry. One of the oldest, because it has been theorized that early hominids were able to develop rapidly due to their ability to heat and mechanically process their food to make it easier to digest. Old, because the ancient Greeks knew that mechanically activating stones (consisting of cinnabar) with vinegar in a copper pestle and mortar caused them to convert into mercury. We might be forgiven for thinking that this could have led our alchemical forbears to wonder if there were other stones that might also be persuaded to convert into gold. Early chemical luminaries such as Michael Faraday and Wilhelm Röntgen dabbled in mechanochemistry. However, in the late 19th and early 20th centuries, the field developed separately in many areas. Perhaps most significantly, synthetic chemists realized that reactions could be carried out with surprisingly high yields and selectivities by shaking them in a ball mill, and that they could even make novel compounds that their colleagues just using heat were not able to. Physicists were mechanically rearranging atoms into new configurations (i.e., doing chemistry) using exotic means such as atomic force microscope tips and optical tweezers. Scientists and engineers studying the formation of lubricious and anti-wear films realized that they were mechanochemically formed. Biochemists found molecular motor proteins, such as myosin and kinesin, that were able to convert chemical energy into motion or, vice versa, mechanical energy into the biochemical energy storage molecule adenosine triphosphate. In 2023, this confluence of advances convinced the Royal Society of Chemistry that the time was ripe to establish a new journal dedicated to the field of mechanochemistry. It is rare that a journal has the privilege of helping to create a new sub-branch of chemistry but, having done so, it has the obligation of helping to define the field and, optimistically, suggesting how the field might develop. This editorial has two major goals. The first is to bring to the attention of the scientific community the challenges faced by the field to set people thinking about how they might contribute and, second, to form the basis for more thorough discussions in the future. The sub-topics below outline current thoughts brought forward from members of our editorial board. We lay out areas and topics here with the intent of establishing a new editorial series, which we invite the community to contribute to, and outline topics and hopefully lay out challenges, which will enable us as a community to come together to move mechanochemistry forward.
KW - Mechanochemistry
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-646086
DO - https://doi.org/10.1039/d4mr90021a
SN - 2976-8683
VL - 2
IS - 1
SP - 10
EP - 19
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-64608
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Belenguer, A
A1 - Michalchuk, Adam
A1 - Lampronti, G
A1 - Sanders, J
T1 - Using solid catalysts in disulfide-based dynamic combinatorial solution- and mechano-chemistry
N2 - We here show for the first time that solid amines can act as catalysts for disulfide-based dynamic combinatorial chemistry by ball mill grinding. The mechanochemical Equilibrium for the two disulfide reactions studied is reached within one to three hours using ten different amine catalysts. This contrasts with the weeks to months to achieve solution equilibrium for most solid amine catalysts at 2%M at 2mM concentration in a suitable solvent. The final mechanochemical equilibrium is independent of the catalyst used, but varies with other ball mill grinding factors such as the presence of traces of solvent. The different efficiencies of the amines tested are discussed.
KW - Mechanochemistry
KW - Green chemistry
KW - Catalysis
PY - 2022
DO - https://doi.org/10.1002/cssc.202102416
SN - 1864-5631
VL - 15
IS - 3
SP - 1
EP - 10
PB - Wiley
AN - OPUS4-53930
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Belenguer, A.
A1 - Lampronti, G.
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
A1 - Sanders, J.
T1 - Quantitative reversible one pot interconversion of three crystalline polymorphs by ball mill grinding
N2 - We demonstrate here using a disulfide system the first example of reversible, selective, and quantitative transformation between three crystalline polymorphs by ball mill grinding. This includes the discovery of a previously unknown polymorph. Each polymorph is reproducibly obtained under well-defined neat or liquid-assisted grinding conditions, revealing subtle control over the apparent thermodynamic stability. We discovered that the presence of a contaminant as low as 1.5% mol mol−1 acting as a template is required to enable all these three polymorph transformations. The relative stabilities of the polymorphs are determined by the sizes of the nanocrystals produced under different conditions and by surface interactions with small amounts of added solvent. For the first time, we show evidence that each of the three polymorphs is obtained with a unique and reproducible crystalline size. This mechanochemical approach gives access to bulk quantities of metastable polymorphs that are inaccessible through recrystallisation.
KW - Mechanochemistry
KW - Polymorph
KW - XRD
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549934
DO - https://doi.org/10.1039/D2CE00393G
SP - 1
EP - 7
PB - Royal Society of Chemistry
AN - OPUS4-54993
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Belenguer, A.
A1 - Michalchuk, Adam
A1 - Lampronti, G
A1 - Sanders, J
T1 - Understanding the unexpected effect of frequency on the kinetics of a covalent reaction under ball-milling conditions
N2 - We here explore how ball-mill-grinding frequency affects the kinetics of a disulfide exchange reaction. Our kinetic data show that the reaction progress is similar at all the frequencies studied (15–30 Hz), including a significant induction time before the nucleation and growth process starts. This indicates that to start the reaction an initial energy accumulation is necessary. Other than mixing, the energy supplied by the mechanical treatment has two effects: (i) reducing the crystal size and (ii) creating defects in the structure. The crystal-breaking process is likely to be dominant at first becoming less important later in the process when the energy supplied is stored at the molecular level as local crystal defects. This accumulation is taken here to be the rate-determining step. We suggest that the local defects accumulate preferentially at or near the crystal surface. Since the total area increases exponentially when the crystal size is reduced by the crystal-breaking process, this can further explain the exponential dependence of the onset time on the milling frequency.
KW - Mechanochemistry
KW - Kinetics
KW - Diffraction
PY - 2019
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-483361
DO - https://doi.org/10.3762/bjoc.15.120
SN - 2195-951X
VL - 15
SP - 1226
EP - 1235
PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften
CY - Frankfurt, M.
AN - OPUS4-48336
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bui, Minh
A1 - Heinekamp, Christian
A1 - Fuhry, Emil
A1 - Weidner, Steffen
A1 - Radnik, Jörg
A1 - Ahrens, Mike
A1 - Scheurell, Kerstin
A1 - Balasubramanian, Kannan
A1 - Emmerling, Franziska
A1 - Braun, Thomas
T1 - Lewis-acid induced mechanochemical degradation of polyvinylidene fluoride: transformation into valuable products
N2 - Polyvinylidene fluoride (–[CH2CF2]n–, PVDF) waste poses significant environmental challenges due to its recalcitrant nature and widespread use. This study addresses the end-of-life management of PVDF by introducing a novel, sustainable mechanochemical approach for its valorisation. We investigated the degradation of PVDF into value-added materials using ball milling with anhydrous AlCl3 to achieve a quantitative mineralisation producing AlF3 and halide-functionalised graphite, along with gaseous products (HCl and CH4). Mechanistic key steps involve Lewis-acid catalysed C–F bond activation, dehydrofluorination and aromatisation. This approach provides an effective solution for PVDF waste management while offering a promising route for the production of high-value materials from polymer waste streams. Our findings contribute to sustainable practices in polymer recycling and resource recovery, respond to pressing environmental concerns associated with fluoropolymer disposal, and demonstrate the potential to convert polymer wastes into useful products.
KW - Mechanochemistry
KW - Polyvinylidenfluoride
KW - Degradation
KW - Ball mill
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649015
DO - https://doi.org/10.1039/d5sc05783c
SN - 2041-6520
VL - 16
IS - 40
SP - 18903
EP - 18910
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-64901
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, C.
A1 - Feiler, Torvid
A1 - Heilmann, Maria
A1 - Braga, D.
A1 - Emmerling, Franziska
A1 - Grepioni, F.
T1 - Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide
N2 - n situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl−, NO3−), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)2(OH2)2(NO3)2] (2) and [Cu(DCD)2(OH2)Cl2]·H2O (4), in addition to the previously known molecular salt [Cu(DCD)2(OH2)2][NO3]2·2H2O (1, DIVWAG) and neutral complex [Cu(DCD)2(OH2)Cl2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA.
KW - Mechanochemistry
KW - In situ
PY - 2022
DO - https://doi.org/10.1039/d1ce01670a
VL - 24
IS - 6
SP - 1292
EP - 1298
PB - RSC
AN - OPUS4-54344
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, L.
A1 - Broll, V.
A1 - Ciurili, S.
A1 - Braga, D.
A1 - Emmerling, Franziska
A1 - Gepioni, F.
T1 - Facilitating Nitrification Inhibition through Green, Mechanochemical Synthesis of a Novel Nitrapyrin Complex
N2 - Nitrapyrin (NP) is applied to cultivated soils to inhibit the enzymatic activity of ammonia monooxygenase (AMO), but its poor aqueous solubility and high volatility severely limit its application. β-Cyclodextrin (β-CD) is commonly used to form inclusion complexes with hydrophobic molecules, improving water solubility and stability upon complexation. Here we report on the mechanochemical synthesis of the inclusion complex β-CD·NP, characterized via a combination of solid-state techniques, including exsitu and in situ X-ray diffraction, Raman and NMR spectroscopies, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The pure inhibitor NP was also structurally characterized. The β-CD·NP complex presents improved solubility and thermal stability, and still inhibits the enzymatic activity of AMO with high efficacy. All results indicate that the inclusion of NP into β-CD represents a viable route for the preparation of a novel class of inhibitors, with improved properties related to stability, water solubility, and good inhibition activity.
KW - Mechanochemistry
KW - Nitrification
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537154
DO - https://doi.org/10.1021/acs.cgd.1c00681
SN - 1528-7505
VL - 21
IS - 10
SP - 5792
EP - 5799
PB - ACS Publications
AN - OPUS4-53715
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 - 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 -
TY - JOUR
A1 - Casali, Lucia
A1 - Carta, Maria
A1 - Michalchuk, Adam
A1 - Delogu, Francesco
A1 - Emmerling, Franziska
T1 - Kinetics of the mechanically induced ibuprofen–nicotinamide co-crystal formation by in situ X-ray diffraction
N2 - Mechanochemistry is drawing attention from the pharmaceutical industry given its potential for sustainable material synthesis and manufacture. Scaling mechanochemical processes to industrial level remains a challenge due to an incomplete understanding of their underlying mechanisms. We here show how time-resolved in situ powder X-ray diffraction data, coupled with analytical kinetic modelling, provides a powerful approach to gain mechanistic insight into mechanochemical reactions. By using the ibuprofen–nicotinamide co-crystal mechanosynthesis as a benchmark system, we investigate the behaviour of the solids involved and identify the factors that promote the reaction. As mechanochemical mechanisms become increasingly clear, it promises to become a breakthrough in the industrial preparation of advanced pharmaceuticals.
KW - Mechanochemistry
KW - Kinetics
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608820
DO - https://doi.org/10.1039/D4CP01457J
SN - 1463-9084
VL - 26
SP - 22041
EP - 22048
PB - Royal Society of Chemistry (RSC)
CY - Cambridge
AN - OPUS4-60882
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Davison, Nathan
A1 - Hemingway, Jack M.
A1 - Wills, Corinne
A1 - Stolar, Tomislav
A1 - Waddell, Paul G.
A1 - Dixon, Casey M.
A1 - Barron, Luke
A1 - Dawson, James A.
A1 - Lu, Erli
T1 - Mechanochemical Synthesis of a Sodium Anion Complex [Na+(2,2,2-cryptand)Na–] and Studies of Its Reactivity: Two-Electron and One-Electron Reductions
N2 - Group 1 metal molecular chemistry is dominated by a +1 oxidation state, while a 0 oxidation state is widespread in the metals. A more exotic, yet still available, oxidation state of group 1 metal is −1, i.e., alkalide. Reported as early as the 1970s, the alkalides appear in every modern inorganic chemistry textbook as an iconic chemical curiosity, yet their reactivity remains unexplored. This is due to their synthetic hurdles. In this work, we report the first facile synthesis of the archetypical alkalide complex, [Na+(2,2,2-cryptand)Na–], which allows us to unveil a versatile reactivity profile of this once exotic species.
KW - Mechanochemistry
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608632
DO - https://doi.org/10.1021/acs.inorgchem.4c02914
VL - 63
IS - 32
SP - 15247
EP - 15258
PB - American Chemical Society (ACS)
AN - OPUS4-60863
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray spectroscopy (XAS)
N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis.
T2 - Denver X-ray Conference: DXC 2021
CY - Online meeting
DA - 02.08.2021
KW - Dispersive XAS
KW - Mechanochemistry
KW - Time resolved
KW - In situ
PY - 2021
AN - OPUS4-56257
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray absorption spectroscopy (XAS)
N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis.
T2 - Advances X ray Analytics Seminar at TU Berlin
CY - Berlin, Germany
DA - 14.06.2022
KW - XAS
KW - Mechanochemistry
KW - Time resolved
KW - In situ
PY - 2022
AN - OPUS4-56259
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray spectroscopy (XAS)
N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis.
T2 - AfLS3
CY - Online meeting
DA - 14.11.2021
KW - Dipsersive XAS
KW - Mechanochemistry
KW - Time-resolved
KW - In situ
PY - 2021
AN - OPUS4-56256
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Cakir, Cafer Tufan
A1 - Radtke, Martin
A1 - Haider, M. Bilal
A1 - Emmerling, Franziska
A1 - F. M. Oliveira, P.
A1 - Michalchuk, Adam
T1 - Dispersive x-ray absorption spectroscopy for time-resolved in situ monitoring of mechanochemical reactions
N2 - X-ray absorption spectroscopy (XAS) provides a unique, atom-specific tool to probe the electronic structure of solids. By surmounting long-held limitations of powder-based XAS using a dynamically averaged powder in a Resonant Acoustic Mixer (RAM), we demonstrate how time-resolved in situ (TRIS) XAS provides unprecedented detail of mechanochemical synthesis. The use of a custom-designed dispersive XAS (DXAS) setup allows us to increase the time resolution over existing fluorescence measurements from ∼15 min to 2 s for a complete absorption spectrum. Hence, we here establish TRIS-XAS as a viable method for studying mechanochemical reactions and sampling reaction kinetics. The generality of our approach is demonstrated through RAM-induced (i) bottom-up Au nanoparticle mechanosynthesis and (ii) the synthesis of a prototypical metal organic framework, ZIF-8. Moreover, we demonstrate that our approach also works with the addition of a stainless steel milling ball, opening the door to using TRIS-DXAS for following conventional ball milling reactions. We expect that our TRIS-DXAS approach will become an essential part of the mechanochemical tool box.
KW - In situ studies
KW - Dipsersive XAS
KW - Mechanochemistry
KW - Time-resolved
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567659
DO - https://doi.org/10.1063/5.0130673
SN - 1089-7690
VL - 157
IS - 21
SP - 1
EP - 12
PB - American Institute of Physics
CY - Melville, NY
AN - OPUS4-56765
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira, P. F. M.
A1 - Torresi, R.
A1 - Emmerling, Franziska
A1 - Carmago, P.
T1 - Challenges and opportunities in the bottom-up mechanochemical synthesis of noble metal nanoparticles
N2 - Mechanochemistry is a promising alternative to solution-based protocols across the chemical sciences, enabling different types of chemistries in solvent-free and environmentally benign conditions. The use of mechanical energy to promote physical and chemical transformations has reached a high level of refinement, allowing for the design of sophisticated molecules and nanostructured materials. Among them, the synthesis of noble metal nanoparticles deserves special attention due to their catalytic applications. In this review, we discuss the recent progress on the development of mechanochemical strategies for the controlled synthesis of noble metal nanostructures. We start by covering the fundamentals of different preparation routes, namely top-down and bottom-up approaches. Next, we focus on the key examples of the mechanochemical synthesis of non-supported and supported metal nanoparticles as well as hybrid nanomaterials containing noble metals. In these examples, in addition to the principles and synthesis mechanisms, their performances in catalysis are discussed. Finally, a perspective of the field is given, where we discuss the opportunities for future work and the challenges of mechanochemical synthesis to produce well-defined noble metal nanoparticles.
KW - Mechanochemistry
KW - Nanoparticles
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512080
DO - https://doi.org/10.1039/D0TA05183G
VL - 8
IS - 32
SP - 16114
AN - OPUS4-51208
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Olivera, Paulo
A1 - Michalchuk, Adam
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Bienert, Ralf
A1 - Torresi, R.
A1 - Camargo, P.
A1 - Emmerling, Franziska
T1 - Tandem X-ray absorption spectroscopy and scattering for in situ time-resolved monitoring of gold nanoparticle mechanosynthesis
N2 - Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.
KW - Mechanochemistry
KW - XANES
KW - X-ray diffraction
KW - Nano particles
PY - 2020
DO - https://doi.org/10.1039/d0cc03862h
SN - 1364-548X
VL - 56
SP - 10329
EP - 10332
PB - Royal Society of Chemistry
AN - OPUS4-51760
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 - CONF
A1 - Emmerling, Franziska
T1 - Shaken not stirred: enhancing the flavor of mechanochemistry
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.2-4 We recently introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy and thermography. The presented setup allows the detection of crystalline, amorphous, eutectic, and liquid intermediates. Furthermore, the chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key for future optimization of mechanochemical syntheses. In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals and coordination polymers.2,3,5 Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemical syntheses.
T2 - BCA/BACG joint spring meeting
CY - Online meeting
DA - 29.03.2021
KW - Mechanochemistry
KW - Cocrystals
KW - Crystal Engineering
PY - 2021
AN - OPUS4-53995
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Shaken not stirred: in situ investigations of mechanochemical processes
N2 - Mechanochemistry has emerged as one of the most interesting synthetic protocols to produce new materials. The development of mechanochemistry as a synthetic method is supported by excellent research by many groups worldwide in a wide range of applications. The potential of mechanochemistry is also reflected in the inclusion in IUPAC’s 10 chemical innovations that will change our world’.[1] Solvent-free methodologies lead to unique chemical processes during synthesis with the consequent formation of martials with new properties.2 In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals, coordination polymers, metal oxides and metal nanoparticles.[3-8] We introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD combined with Raman spectroscopy and thermography.
T2 - Deutsche Kristallzüchtertagung
CY - Berlin, Germany
DA - 06.10.2021
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Crystal
PY - 2021
AN - OPUS4-53996
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 - Mechanochemical formation of multicomponent crystal systems: Mechanism & Kinetics
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. 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 the mechanochemical reactivity and selectivity.
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 adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.
Here we will discuss our recent results investigating the formation of (poly-morphic) cocrystals, metal-organic compounds, and salts, thereby elucidating the influence of milling parameters 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 investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 25th International Conference on the Chemistry of the Organic Solid State (ICCOSS XXV)
CY - Ohrid, Macedonia
DA - 03.07.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Crystal Engineering
PY - 2022
AN - OPUS4-55413
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemical formation of multicomponent crystals systems
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. 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.
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, metal-organic compounds, and salts, thereby elucidating the influence of milling parameters and reaction sequences on the formation mechanism and kinetics. Our results indicate that time-resolved in situ investigations of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 5ECQUL Forging Bonds
CY - Lisbon, Portugal
DA - 12.07.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - N-Chlorination
PY - 2022
AN - OPUS4-55414
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Shaken not stirred: enhancing the flavor of mechanochemistry
N2 - compounds and cocrystals. The ever-increasing interest in this method is contrasted by a limited mechanistic understanding of the mechanochemical reactivity and selectivity. 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. Time-resolved in situ investigations of milling reactions (Figure 1) provide direct insights into the underlying mechanisms. We recently introduced different setups enabling in situ investigation of mechanochemical reactions using synchrotron XRD and XAS combined with Raman spectroscopy and thermography. The presented setup allows the detection of crystalline, amorphous, eutectic, and liquid intermediates. Furthermore, the chemical composition of the reaction mixture was found to be directly correlated with changes in the temperature profile of the reaction. The resulting deeper kinetic and thermodynamic understanding of milling processes is the key to future optimization of mechanochemical syntheses. In this contribution, we will discuss our recent results investigating the formation of (polymorphic) cocrystals and coordination polymers. Our results indicate that time-resolved in situ investigations of mechanochemical processes are key for tuning and optimizing mechanochemical syntheses allowing to unleash the potential of mechanochemistry for a green materials design.
T2 - 2nd National Crystallographic Meeting Lisbon, Portugal
CY - Lisbon, Portugal
DA - 15.07.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Crystal
PY - 2022
AN - OPUS4-55415
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - Mechanochemical formation of multicomponent crystal systems: Mechanism & Kinetics
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. 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 the mechanochemical reactivity and selectivity. 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 adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.1 Here we will discuss our recent results investigating the formation of (polymorphic) cocrystals2–3 and metal-organic frameworks,4 thereby elucidating the influence of milling parameters 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.6 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 investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - 10th International conference on Mechanochemistry and Mechanical Alloying
CY - Cagliari, Italy
DA - 06.06.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Cocrystal
PY - 2022
AN - OPUS4-55421
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 - Why shaken, not stirred, makes the difference: insights into mechanochemical reactions from in situ investigations
N2 - Mechanochemistry is an effective, environmentally benign, and facile method for the synthesis of new multicomponent crystal systems. 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 the mechanochemical reactivity and selectivity.
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 adsorption spectroscopy, NMR, Raman spectroscopy, and thermography.
Here we will discuss our recent results investigating the formation of (poly-morphic) cocrystals[1,3], metal-organic compounds, and salts, thereby elucidating the influence of milling parameters 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 investigation of milling reactions offer a new approach to tune and optimize mechanochemical processes.
T2 - GdCh Vortrag Universität Potsdam
CY - Potsdam, Germany
DA - 05.06.2023
KW - Mechanochemistry
KW - In Situ
PY - 2023
AN - OPUS4-58982
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 - 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 - 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 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical reactions - new insights in formation pathways
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 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 situ Raman spectroscopy coupled with thermography revealed a low temperature increase during milling reactions due to the mechanical impact and clear temperature increases because of the reaction heat.
Based on the data, temperature rises as postulated in the magma plasma and hot spot theory can be excluded for soft matter milling syntheses. Our results indicate that in situ investigation of milling reactions offer a new approach to tune and optimize mechanochemically synthesized compounds.
T2 - Wissenschaftsforum Chemie
CY - Berlin, Germany
DA - 10.09.17
KW - Mechanochemistry
KW - In situ
PY - 2017
AN - OPUS4-43563
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 -