RSC Mechanochemistry最新文献

{"title":"Mechanochemical synthesis of β-cyclodextrin urea derivatives under reactive CO2 atmosphere by Staudinger aza-Wittig reaction†","authors":"Sawssen Nasri, Maxime Lestoquoy, Anne Ponchel, Eric Monflier and Stéphane Menuel","doi":"10.1039/D4MR00020J","DOIUrl":"https://doi.org/10.1039/D4MR00020J","url":null,"abstract":"<p >Various ureido β-cyclodextrins can be easily synthesised by mechanochemistry from azido-β-cyclodextrins, carbon dioxide and amino derivatives. The reaction was carried out with short reaction times, without solvents and without thermal activation, greatly reducing the environmental impact of the synthesis.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00020j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A hybrid density functional study on the mechanochemistry of silicon carbide nanotubes","authors":"Aabiskar Bhusal, Kapil Adhikari and Qian Sun","doi":"10.1039/D4MR00043A","DOIUrl":"https://doi.org/10.1039/D4MR00043A","url":null,"abstract":"<p >The constrained geometries simulate the external force (CoGEF) method mimics the application of external stress on molecules. Herein, we used the CoGEF method at the hybrid density functional theory level to investigate the behavior of silicon carbide nanotubes (SiCNTs) under longitudinal stress. When the SiCNTs are under longitudinal stress, we observe a gradual decrease in the binding energy and the frontier orbital gap with the applied strain until a critical threshold is reached. Beyond this threshold, a sudden increase in both parameters occurs, indicating the formation of some kind of stable structure. The higher binding energy of the larger SiCNTs makes them more resistant to rupture under strain, suggesting their increased mechanical strength. Additionally, we observed a rapid initial increase of Young's modulus of SiCNTs and convergence to a constant magnitude with further increase in their diameter. Therefore, CoGEF analysis provides invaluable insights into the changes occurring in the structural and electronic properties of SiCNTs when subjected to stress.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00043a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revealing the mechanism of reductive, mechanochemical Li recycling from LiFePO4†","authors":"David Geiß, Oleksandr Dolotko, Sylvio Indris, Christian Neemann, Andrei Bologa, Thomas Bergfeldt, Michael Knapp and Helmut Ehrenberg","doi":"10.1039/D4MR00014E","DOIUrl":"https://doi.org/10.1039/D4MR00014E","url":null,"abstract":"<p >In order to mitigate the risks associated with cobalt supply, a safe and affordable LiFePO<small>₄</small>-based (LFP) cathode for Li-ion batteries can be a significant solution to meet the rapidly growing battery market. However, economical and environmentally friendly recycling of LFP is impossible with currently available recycling technologies. In this study, an acid-free mechanochemical approach is applied to reclaim Li from LFP using Al as a reducing agent. The reaction mechanism involved in reductive ball-milling followed by water leaching has been elucidated through the examination of various milling times and molar ratios of components, fostering a deeper understanding of the process. Assessing the yield and purity of the final products provides insights into potential enhancements for this technology. Utilizing Al as the material of the current collector eliminates the need for additional external additives, thereby simplifying the recycling workflow. Continued research into this process has the potential to facilitate efficient and economical recycling of LFP materials.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00014e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanochemical synthesis of Zn-bionanohybrids: size effect at the nanoscale to improve their enzyme-like activity†","authors":"Carla Garcia-Sanz, Laura Guijarro, Mirosława Pawlyta and Jose M. Palomo","doi":"10.1039/D4MR00019F","DOIUrl":"https://doi.org/10.1039/D4MR00019F","url":null,"abstract":"<p >The mechanochemical synthesis of nanomaterials for catalytic applications is a growing research field owing to its simplicity, scalability, and eco-friendliness. In this work, we synthesised new zinc bionanohybrids <em>via</em> a mechanochemical method involving a size effect at the nanoscale and microscale levels of the final nanostructure. This effect translates into an improvement in the catalytic properties of this nanomaterial, such as enzyme-like activities, compared to that synthesized in an aqueous media. One-pot synthesis was performed by combining <em>Candida antarctica</em> lipase B (CALB) solution, solid zinc salts and phosphate or bicarbonate salts using the ball-milling approach, where overall reaction times were drastically reduced in comparison with the traditional aqueous method. The reaction was carried out at r.t. and the synthesis process was evaluated by considering the use of steel balls with different sizes, completely dry conditions or in the presence of a very small amount of water as an additive (2 mL), and incubation methods (planetary or horizontal ball milling). The final nanostructure of the Zn biohybrids was determined using XRD, FT-IR, TEM and SEM analysis, demonstrating changes in metal species and drastic changes in the nanostructure conformation of the biohybrids obtained through the mechanical approach compared to those obtained through the aqueous method. The size effect at the nanoscale was also demonstrated in the final species, showing a reduced size. This nanoscale effect of the material had a positive impact on the catalytic properties of the materials, in some cases showing up to 2000 times greater activity compared to the counterpart synthesised under aqueous conditions.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00019f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanochemical synthesis and application of mixed-metal copper–ruthenium HKUST-1 metal–organic frameworks in the electrocatalytic oxygen evolution reaction†","authors":"Linda Sondermann, Quentin Smith, Till Strothmann, Annette Vollrath, Thi Hai Yen Beglau and Christoph Janiak","doi":"10.1039/D4MR00021H","DOIUrl":"https://doi.org/10.1039/D4MR00021H","url":null,"abstract":"<p >Novel electrode materials for electrocatalytic hydrogen generation are investigated for increasing the activity of expensive noble-metal components. Here various mixed-metal copper–ruthenium combinations of the metal–organic framework (MOF) HKUST-1 (HKUST = Hong Kong University of Science and Technology, with the formula [Cu<small>₃</small>(BTC)<small>₂</small>(H<small>₂</small>O)<small>₃</small>]<small>_<em>n</em></small> (BTC = benzene-1,3,5-tricarboxylate)) as Cu<small>_<em>x</em></small>Ru-BTC were synthesized through a mechanochemical method. This mechanochemical method allowed for gram-scale synthesis of the mixed-metal MOFs in a one-hour synthesis time. Characterization through powder X-ray diffraction (PXRD), N<small>₂</small>-adsorption, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier transform infrared (FT-IR) spectroscopy confirmed the formation of a MOF with the HKUST-1 topology, albeit with lower porosity compared to neat HKUST-1. The synthesized MOFs were tested as precursor materials for catalysts for the oxygen evolution reaction (OER) and performed comparably to the industry standard ruthenium oxide (RuO<small>₂</small>). An overpotential (<em>η</em>) of 314 mV (RuO<small>₂</small><em>η</em> = 312 mV), a Tafel slope (<em>b</em>) of 55 mV dec<small>⁻¹</small> (RuO<small>₂</small><em>b</em> = 47 mV dec<small>⁻¹</small>) was achieved which in combination with a charge-transfer resistance (<em>R</em><small>_CT</small>) of 13.6 Ω (RuO<small>₂</small><em>R</em><small>_CT</small> = 52.8 Ω) and a faradaic efficiency (FE) of 70% (RuO<small>₂</small> FE = 66%) supports the derived catalyst from Cu<small>₁₀</small>Ru-BTC with an intimate mixture of copper and ruthenium at the nanoscale to be effective for the OER having lower ruthenium content than RuO<small>₂</small>. All derived catalysts from the Cu<small>_<em>x</em></small>Ru-BTC samples and RuO<small>₂</small> showed good stability in a chronopotentiometric measurement over 12 h.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00021h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Al2O3 promoted mechanochemical nucleophilic aromatic substitution†","authors":"Luca Vaghi, Eva Palomba and Antonio Papagni","doi":"10.1039/D4MR00039K","DOIUrl":"https://doi.org/10.1039/D4MR00039K","url":null,"abstract":"<p >An auxiliary mediated solventless mechanochemical methodology for the nucleophilic aromatic substitution of aryl fluorides by nitrogen nucleophiles without the aid of any base has been developed. The excellent affinity of Al<small>₂</small>O<small>₃</small> for hydrogen fluoride is the key for this process. Thanks to the use of Al<small>₂</small>O<small>₃</small> as a milling auxiliary yields of up to 99% were achieved, and the easily processable crude derived from the milling jar allowed a simple and fast work-up procedure, making this method very attractive.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00039k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142165142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Completely solvent-free synthesis of double heterohelicenes and their further ring fusion using mechanochemical reaction†","authors":"Honoka Sada, Daisuke Sakamaki, Masayuki Gon, Kazuo Tanaka, Takashi Hirose and Hideki Fujiwara","doi":"10.1039/D4MR00033A","DOIUrl":"https://doi.org/10.1039/D4MR00033A","url":null,"abstract":"<p >In this study, we developed a simple and efficient method for synthesizing double heterohelicenes (DHHs) composed of two heteroacenes bearing an NH group, such as benzo[<em>b</em>]phenoxazine (<strong>BPO</strong>) and dibenzo[<em>b</em>,<em>i</em>]phenoxazines (<strong>DBPO</strong>), using mechanochemical oxidative C–N coupling reactions, allowing complete solvent-free synthesis from commercially available compounds. Our new synthetic method afforded more than 1 g of DHH, which has a high dissymmetry factor for circularly polarized luminescence (<em>g</em><small>_CPL</small>) of &gt;1 × 10<small>⁻²</small>, in a one-pot mechanochemical reaction using <strong>BPO</strong> as a reactant. In addition, mechanochemical oxidative coupling also allows for further fusion reactions of DHHs, leading to semi- or fully planarized molecules, which have not been previously achieved through solution-phase reactions. We isolated semi-planarized heterohelicenes <strong>5</strong> and <strong>6</strong> and determined their structures using single-crystal X-ray analysis. Compounds <strong>5</strong> and <strong>6</strong> exhibited enhanced electron donor properties compared to DHHs <strong>3</strong> and <strong>4</strong>. The enantiomers of <strong>6</strong> exhibited clear CPL emissions with a |<em>g</em><small>_CPL</small>| value of 2 × 10<small>⁻³</small>. The magnitudes of the transition magnetic dipole moment (TMDM) of <strong>5</strong> and <strong>6</strong> increased compared to those of <strong>3</strong> and <strong>4</strong>. Transition moment density analysis revealed that large TMDM densities appeared on the newly formed C–C bonds, providing a unique molecular design guideline for enhancing the magnitude of the TMDM without expanding the molecular structure.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00033a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The role of the milling environment on the copper-catalysed mechanochemical synthesis of tolbutamide†","authors":"Kathleen Floyd, Lori Gonnet, Tomislav Friščić and James Batteas","doi":"10.1039/D4MR00031E","DOIUrl":"https://doi.org/10.1039/D4MR00031E","url":null,"abstract":"<p >We provide a systematic investigation of the role of atmospheric oxygen and choice of milling assembly (<em>i.e.</em>, the milling jar and ball materials) on a prototypical medicinal mechanochemistry reaction: the copper-catalysed coupling of isocyanate and sulfonamide to form the sulfonylurea tolbutamide. Using in-house developed equipment for work under controlled-atmosphere milling conditions, we reveal that the reaction is in fact catalysed by Cu(<small>II</small>) species, with the conventionally used CuCl acting as a pre-catalyst, which becomes activated <em>via</em> aerobic oxidation during milling. Unexpectedly, the choice of milling jar material was found to have a profound effect on the coupling, with aluminium jars effectively “shutting down” reactivity, most likely by preventing CuCl oxidation. Hence, opposite to direct mechanocatalysis, a term used to describe reactions promoted by the milling jar or ball material, this observation reveals the possibility of direct mechanoinhibition – <em>i.e.</em>, the inhibition of a mechanochemical reaction by the jar. These results highlight the importance of systematic investigations of both the milling assembly, as well as atmosphere, in understanding and controlling organic mechanochemical transformations.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00031e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanochemical synthesis of zinc-doped hydroxyapatite for tunable micronutrient release†","authors":"Mohamed Ammar, Ricardo Bortoletto-Santos, Caue Ribeiro, Lihua Zhang and Jonas Baltrusaitis","doi":"10.1039/D3MR00012E","DOIUrl":"https://doi.org/10.1039/D3MR00012E","url":null,"abstract":"<p >Mechanochemical synthesis of Zn-laden calcium hydroxyapatite (HAP) nanocrystals was performed from a chemically precipitated monetite/brushite precursor. ZnCO<small>₃</small> served as the Zn<small>²⁺</small> source. Powder XRD results showed that up to 15% ZnCO<small>₃</small> can be incorporated into the HAP lattice during the mechanochemical transformation of the precursors. The resulting spectral properties, as investigated using Raman and infrared spectroscopy, showed stark differences between the mechanochemically prepared sample and the control HAP and ZnCO<small>₃</small> mixed sample. In particular, a peak at 874 cm<small>⁻¹</small> was observed in infrared and assigned to the HAP-incorporated carbonate ion C–O (<em>ν</em><small>₂</small>) vibration as opposed to ZnCO<small>₃</small> at 834 cm<small>⁻¹</small> indicating that not only Zn<small>²⁺</small> but also CO<small>₃</small><small>²⁻</small> is incorporated into the HAP lattice. Distinct thermal properties were also observed in the thermal analysis of mechanochemically reacted Zn-HAP with the endothermic peak at 235 °C completely absent as opposed to the mixed control of HAP and ZnCO<small>₃</small>. Electron microscopy analysis showed ∼10 × 40 nm HAP nanocrystals formed with a uniform Zn<small>²⁺</small> ion distribution within them, especially at low 5% ZnCO<small>₃</small> loading. Zn<small>²⁺</small> dissolution experiments in soil-relevant 2% citric acid solution showed a distinct delayed dissolution pattern of mechanochemically obtained Zn-HAP with six-fold slower dissolution than that of mixed HAP and ZnCO<small>₃</small>, a commonly used zinc supplement. This study presents room-temperature synthesis methods of plant nutrient-laden HAP with tunable dissolution kinetics needed for efficient nutrient uptake.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00012e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanochemical synthesis of bismuth active pharmaceutical ingredients, bismuth(iii) gallate and bismuth citrate†","authors":"Daniel Szczerba, Jean-Louis Do, Davin Tan, Hatem M. Titi, Nicolas Geoffroy, María del Carmen Marco de Lucas, Julien Boudon, Ivan Halasz, Tomislav Friščić and Simon A. J. Kimber","doi":"10.1039/D4MR00008K","DOIUrl":"https://doi.org/10.1039/D4MR00008K","url":null,"abstract":"<p >Organobismuth compounds have been known for centuries as substances of medical interest, and continue to be used in medicine today. Bismuth active pharmaceutical ingredients (APIs) are used as digestive aids, including in combating <em>Helicobacter pylori</em>, showing antiviral properties. Here we report the mechanochemical synthesis of bismuth gallate and bismuth citrate. In addition, we revisit the previously reported mechanochemical synthesis of bismuth(<small>III</small>) di- and trisalicylate. In the case of bismuth citrate, which has an unknown structure, we show that hydration induces a reversible transformation to a large (possibly cubic) unit cell.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00008k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}