RSC Mechanochemistry最新文献

{"title":"Mechanochemical route to high-purity halide perovskites with real-time temperature tracking","authors":"Raphael Neisius, Paola Ragonese, Isabel Gonçalves, Teresa Gatti and Isabella Poli","doi":"10.1039/D5MR00085H","DOIUrl":"https://doi.org/10.1039/D5MR00085H","url":null,"abstract":"<p >Mechanochemical synthesis is a sustainable and scalable approach for producing halide perovskites, offering key advantages over traditional solution-based methods, such as solvent-free processing, improved stoichiometric control, and reduced toxicity. In this work, we present a detailed study on the mechanochemical synthesis of MAPbI<small>₃</small> and MAPbBr<small>₃</small> (MA = methylammonium), with real-time monitoring of temperature developed to optimize the grinding conditions. We find that the temperature increase primarily originates from mechanical impact rather than the exothermicity of the reaction and does not limit perovskite formation and quality. Ultra-pure MAPbI<small>₃</small> is readily obtained in under 10 minutes, while MAPbBr<small>₃</small> requires longer grinding times for complete conversion (30 min). Prolonged milling yields finer powders, which are essential for formulating well-dispersed, DMF-free inks. These inks enable the fabrication of one-step slot-die coated perovskite photodetectors under ambient conditions. Our findings highlight that real-time thermal diagnostics provides a valuable tool for optimizing mechanochemical synthesis protocols and the importance of powder refinement to achieve homogeneous films suitable for scalable optoelectronic applications.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 1","pages":" 83-91"},"PeriodicalIF":0.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/mr/d5mr00085h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950622","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":"Exploring milling atmosphere effects in mechanochemical synthesis of Pd–Cu supported catalysts for the semihydrogenation of acetylene in equimolar ethylene mixtures","authors":"Rohini Khobragade, Jonathan M. Mauß, Nguyen Khang Tran and Ferdi Schüth","doi":"10.1039/D5MR00074B","DOIUrl":"https://doi.org/10.1039/D5MR00074B","url":null,"abstract":"<p >Supported bimetallic nanoparticles (NPs) have evolved as promising candidates for heterogeneous catalysis. Among various synthesis methods, ball milling has recently emerged as an effective approach for the preparation of high performing catalysts in diverse applications. Recognizing that solid–gas interactions in such a solvent-free environment might be crucial, we investigated the influence of the gas atmosphere (oxidative, inert, and reductive) during ball milling on the structural and electronic properties of Pd–Cu alloy NPs supported on high surface area α-Al<small>₂</small>O<small>₃</small>. Milling under an oxidative atmosphere leads to Cu-segregation to the surface, forming CuO, PdO, and a small fraction of metallic Pd alongside the Pd–Cu alloy phase. In contrast, in the case of an inert atmosphere, the major phase is the Pd–Cu alloy with a very minimal fraction of unalloyed metallic components. Milling under a reductive atmosphere reveals reverse segregation with metallic Pd segregating to the surface. Additional thermal treatment further promotes the alloy formation in all cases, but oxide species from synthesis under oxidative atmosphere are retained. Unveiling structure–property correlations, the materials were tested in the catalytic selective hydrogenation of acetylene to ethylene in equimolar acetylene/ethylene mixtures under industrially relevant pressure. Results demonstrate that the ball-milling atmosphere significantly influences catalytic performance, driven by the structural and electronic variations induced during synthesis. This study underscores the critical role gas environments may have in mechanochemical processes and highlights their potential to fine-tune catalyst properties for improved performance.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 923-935"},"PeriodicalIF":0.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00074b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374746","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":"Mechanoradical-driven C–H halogenation and nitration of arenes and vicinal dibromination of alkenes in the solid state","authors":"Yongjie Jiang, Xiang Gu, Taoyong Wang and KaKing Yan","doi":"10.1039/D5MR00094G","DOIUrl":"https://doi.org/10.1039/D5MR00094G","url":null,"abstract":"<p >We report a solvent-free mechanochemical approach for the C–H halogenation and nitration of arenes. <em>In situ</em>-generated oxygen-centered mechanoradicals readily oxidize halide or nitrite salts, enabling C–H functionalization of arenes. Radical trapping experiments confirm the involvement of bromine radical species, distinct from conventional solution-phase processes that predominantly proceed <em>via</em> brominium intermediates. This operationally simple and carbon-free strategy is further extended to solid-state vicinal dibromination reactions of unactivated alkenes.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 1","pages":" 27-32"},"PeriodicalIF":0.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/mr/d5mr00094g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950575","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":"Experimental quantification of impact force and energy for mechanical activation in vibratory ball mills","authors":"Emmanuel Nwoye, Kathleen Floyd, James Batteas and Jonathan Felts","doi":"10.1039/D5MR00059A","DOIUrl":"https://doi.org/10.1039/D5MR00059A","url":null,"abstract":"<p >Mechanochemistry has been shown to provide a greener alternative to chemical synthesis; however, challenges in establishing clear relationships between chemical reaction yields and operational reactor parameters, such as milling frequency, milling ball material properties, vessel material properties, and reactor geometries used in a mechanochemical synthesis, make optimizing reactor efficiency difficult. This study presents a force model that relates these reactor parameters to quantifiable impact forces within a vibratory ball mill. To validate this force model, we developed a method for integrated, real-time measurement of force ensembles in the reaction vessel by embedding piezoresistive sensors with fast response to capture impact dynamics at various milling frequencies and operational settings. We measured force using preground NaCl at different fill ratios and compared it to an adjusted Hertzian contact mechanics force model with fill factor. We found agreement between the measured and modeled impact force. At the macroscale, impact acts as an ensemble of forces dynamically applied to the reactants. By simulating the mechanical activation of an illustrative mechanochemical system with known energetics, we show that there is little to no difference in effect between using the mean impact force and force ensemble on the kinetics of a straightforward mechanochemical reaction. We also demonstrate kinetic energy quantification in the Knoevenagel condensation reaction of vanillin and barbituric acid to understand what fraction of kinetic energy goes toward mechanical activation. We observed that the energetics of high-frequency milling for this reaction system entail diminishing returns, reinforcing the notion that there can be an optimal balance between collision intensity, resulting impact forces, and productive energy usage. The developed toolset and models provide a framework for understanding mechanochemical activation in vibratory ball mills and optimizing reaction parameters for scale-up to other reactors.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 911-922"},"PeriodicalIF":0.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00059a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374747","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":"Synthesis of cyclic carbonates via silver-catalysed fixation of CO2 to propargyl alcohols under mechanochemical conditions","authors":"Naohito Tomita, Hironao Sajiki and Takashi Ikawa","doi":"10.1039/D5MR00072F","DOIUrl":"https://doi.org/10.1039/D5MR00072F","url":null,"abstract":"<p >This paper describes the development of a mechanochemical method for the synthesis of cyclic carbonate esters <em>via</em> CO<small>₂</small> fixation on propargyl alcohols. This solvent-free process is rapid and occurs under ambient conditions, thus offering a sustainable and efficient alternative to conventional solvent-based protocols. The mechanochemistry, which utilises the energy generated from milling, has the advantage of minimising waste, reducing reaction times, and simplifying work-up. The developed protocol demonstrates broad functional group tolerance, high yields, and the elimination of complex setups, thus highlighting its potential for application in organic and pharmaceutical synthesis.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 809-812"},"PeriodicalIF":0.0,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00072f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374764","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":"Linking mechanics and chemistry: machine learning for yield prediction in NaBH4 mechanochemical regeneration","authors":"Santiago Garrido Nuñez, Dingena L. Schott and Johan T. Padding","doi":"10.1039/D5MR00076A","DOIUrl":"https://doi.org/10.1039/D5MR00076A","url":null,"abstract":"<p >Mechanochemical synthesis faces reproducibility and scale-up challenges due to complex parameter interactions. This study employs machine learning (ML) to predict NaBH<small>₄</small> regeneration yield, integrating chemical experimental data and DEM (Discrete Element Method) derived invariant mechanical descriptors (<em>Ē</em><small>_n</small>, <em>Ē</em><small>_t</small>, <em>f</em><small>_col</small>/<em>n</em><small>_ball</small>). Various algorithms were evaluated, including a two-step modeling strategy to isolate the dominant effect of milling time in our process. Results demonstrate that a two-step Gaussian Process Regression (GPR) model achieves good predictive performance (<em>R</em><small>²</small> = 0.83), significantly outperforming single-stage models and providing valuable uncertainty estimates. Tree-based ensembles (XGBoost, RF) also benefit from the two-step approach and can enhance interpretability. This work establishes a framework for using ML to optimize mechanochemical processes, reducing experimental cost and offering a method to link mechanical milling conditions to chemical outcomes, thereby enabling predictive mechanochemistry.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 889-900"},"PeriodicalIF":0.0,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00076a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374772","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":"X-ray diffraction study of the polymorphism in Er2O3 driven by ball milling","authors":"Ana Maria Constantin, Francesco Mele, Daniele Alessandro Cauzzi, Raimondo Maggi, Elena Villa, Alessandro Cerveri and Lara Righi","doi":"10.1039/D5MR00033E","DOIUrl":"https://doi.org/10.1039/D5MR00033E","url":null,"abstract":"<p >Polymorphic transformations in rare-earth sesquioxides (RE-SOs) are accessible <em>via</em> ball-milling. Prolonged mechanical grinding induces the formation of denser polymorphic structures, replicating the phenomena typically observed under high-pressure conditions. In this study, Er<small>₂</small>O<small>₃</small> cubic phase with bixbyite structure (C-type) was subjected to different milling sessions with diverse vibrational milling frequencies. X-ray diffraction experiments combined with Williamson–Hall (W–H) and Rietveld analysis were adopted to study the microstructural aspects encompassing crystal size, microstrain, and unit cell distortion. As the frequency increased, the transition from the Er<small>₂</small>O<small>₃</small> cubic to the monoclinic denser structure (B-type) was partially activated. When the milling frequency reached the critical condition, the polymorphic transformation was completely realized. The analysis of the microstructural changes triggered by high frequency milling discloses the key-role of the microstrain, rather than the reduction of the crystal size, in driving the structural transition from cubic to monoclinic polymorphs. Furthermore, ball milling conducted at the highest frequency promotes, rather than amorphization, the formation of the polymorphic form exhibiting a fluorite (CaF<small>₂</small>)-type structure, indicating the presence of point lattice defects involving oxygen vacancies. As a result, the structural analysis revealed the distinct role of microstructural features in promoting polymorphism within RE-SOs.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 901-910"},"PeriodicalIF":0.0,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00033e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374773","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 conversion of elemental sulfur into functional sulfur nanomaterials for promising applications","authors":"Hammad Hasan, Farwa Arshad and Md Palashuddin Sk","doi":"10.1039/D5MR00051C","DOIUrl":"https://doi.org/10.1039/D5MR00051C","url":null,"abstract":"<p >This review highlights the growing role of mechanochemistry in the synthesis and functionalization of sulfur-based nanomaterials. It begins with a conceptual and historical overview of mechanochemical processes, emphasizing how mechanical energy enables selective bond cleavage, defect formation, and structural transformations in solids. Particular focus is placed on the mechanochemical synthesis of sulfur nanomaterials, where mechanical activation overcomes the inherent chemical inertness of elemental sulfur, promoting the formation of nanodots and other nanostructures. Subsequent sections explore the structural, optical, and photophysical properties of these materials, including light absorption, photoluminescence (PL), optical stability, time-resolved photoluminescence (TRPL), and circularly polarized luminescence (CPL). These properties are strongly influenced by stress-induced defects and crystallinity, which are hallmark features of the mechanochemical approach. The review further surveys a range of application areas such as sensing, catalysis, and energy conversion, where sulfur nanomaterials exhibit promising performance owing to their unique physicochemical properties. In conclusion, we address current challenges, including defect control and the need for a deeper mechanistic understanding, and propose future directions for expanding the scope and enhancing the utility of mechanochemical methods in nanochemistry. Overall, this work underscores the potential of mechanochemistry not only as a green, solvent-free synthesis strategy but also as a powerful platform for uncovering novel functionalities in sulfur-based nanomaterials.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 786-801"},"PeriodicalIF":0.0,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00051c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374762","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":"Structure–performance relationships of mechanochemically synthesized piezoelectric catalysts BaTiO3, NaNbO3 and BiFeO3","authors":"Erin V. Phillips, Van Son Nguyen, Marta Hatzell and Carsten Sievers","doi":"10.1039/D5MR00062A","DOIUrl":"https://doi.org/10.1039/D5MR00062A","url":null,"abstract":"<p >Piezoelectric catalysts were synthesized mechanochemically by converting BaCO<small>₃</small> and TiO<small>₂</small> to BaTiO<small>₃</small>, Na<small>₂</small>CO<small>₃</small> and Nb<small>₂</small>O<small>₅</small> to NaNbO<small>₃</small> and Bi<small>₂</small>O<small>₃</small> and Fe<small>₂</small>O<small>₃</small> to BiFeO<small>₃</small>. The catalytic reactivity of BaTiO<small>₃</small>, NaNbO<small>₃</small> and BiFeO<small>₃</small> was tested using a mechanocatalytic arylation reaction involving 4-nitrobenzenediazonium tetrafluoroborate. The observed activity in the arylation reaction showed a dependence on the abundance of piezoelectrically active anisotropic phases as measured by the pre-edge intensity in XANES spectra of BaTiO<small>₃</small> and NaNbO<small>₃</small> and distribution of crystalline phases as measured by XRD for BiFeO<small>₃</small>. A kinetic analysis showed that the reaction over BaTiO<small>₃</small> was limited by the amount of diazonium salt remaining in the reaction vessel, while the reaction over NaNbO<small>₃</small> and BiFeO<small>₃</small> was limited by the generation of electron hole pairs within the piezoelectric structure. This work shows that mechanochemically produced piezocatalysts have superior structural characteristics such as greater relative abundance of anisotropic phases, higher surface areas and smaller particle sizes that led the mechanochemically produced catalysts to outperform piezoelectric commercial counterparts when tested under the same arylation milling conditions.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 864-878"},"PeriodicalIF":0.0,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00062a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374770","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":"Mechanically induced sequential one-pot Wittig olefination–Diels–Alder reaction: a solvent-free approach to complex bicyclic scaffolds","authors":"Nina Biedermann and Michael Schnürch","doi":"10.1039/D5MR00087D","DOIUrl":"https://doi.org/10.1039/D5MR00087D","url":null,"abstract":"<p >Herein we present a mechanically induced, solvent-free protocol that sequentially combines the Wittig olefination and Diels–Alder cycloaddition in one-pot and enables the synthesis of structurally complex bicyclic compounds. This method proceeds entirely under ball milling conditions without the requirement of any solvent while eliminating the need for intermediate purification. Careful optimization of the milling parameters and reagent addition enables efficient conversion of various α,β-unsaturated aldehydes and ketones with electron-deficient dienophiles to the corresponding cycloadducts <em>via</em> diene intermediates, demonstrating high stereoselectivity and yielding exclusively <em>endo</em> Diels–Alder adducts. Furthermore, the extension of the sequence by a solvent-free one-pot oxidation is exemplified, achieving a three-step synthesis in a single milling vessel without intermediate workup and purification, which exhibits excellent green metrics in comparison with solution-based methods. This operationally simple and sustainable approach demonstrates the potential of mechanochemistry to streamline multistep organic synthesis, while reducing solvent use and energy demand.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":" 6","pages":" 879-888"},"PeriodicalIF":0.0,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/mr/d5mr00087d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145374771","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}