Hinojosa Steffi Krause, Dogan Tugce, Fabig Sven, Grätz Sven, Borchardt Lars
Inorganic Chemistry I, Ruhr-University Bochum, Universitätstraße 150, Bochum, 44801, Germany.
Chemistry. 2025 Aug 26;31(48):e01336. doi: 10.1002/chem.202501336. Epub 2025 Aug 8.
Mechanochemical processes have traditionally been explored using ball mills; however, resonant acoustic mixers (RAM) offer a compelling alternative, operating without milling media and enabling scalable, solvent-free synthesis. Despite their advantages, direct transfer of reaction conditions from ball mills to RAM has proven nontrivial, requiring careful optimization of key parameters. In this study, we systematically define an operational window for effective in situ Raman monitoring in RAM. Critical parameters-including vessel material, applied gravitational force, filling degree, substrate rheology, and reaction time-were assessed to ensure high-quality spectral acquisition. Utilizing a sapphire-glass window and a precisely aligned laser setup, we achieved strong, reproducible Raman signals under controlled conditions. The optimal window was found to include a minimum filling degree of 10% and applied g-forces between 20 and 70 g. This framework was validated across diverse mechanochemical reactions, including organic condensations (Knoevenagel and quinoxaline), metal-organic framework formation (ZIF), and catalytic coupling (Glaser reaction), demonstrating the robustness and versatility of in situ Raman spectroscopy in RAM-based synthesis.
传统上,机械化学过程是使用球磨机进行探索的;然而,共振声学混合器(RAM)提供了一种引人注目的替代方法,它无需研磨介质即可运行,并能实现可扩展的无溶剂合成。尽管它们具有优势,但将反应条件从球磨机直接转移到RAM已证明并非易事,需要仔细优化关键参数。在本研究中,我们系统地定义了在RAM中进行有效原位拉曼监测的操作窗口。评估了包括容器材料、施加的重力、填充度、底物流变学和反应时间在内的关键参数,以确保高质量的光谱采集。利用蓝宝石玻璃窗口和精确对准的激光装置,我们在受控条件下获得了强烈、可重复的拉曼信号。发现最佳窗口包括最低10%的填充度和20至70 g之间的施加重力。该框架在各种机械化学反应中得到了验证,包括有机缩合反应(克诺文纳格尔反应和喹喔啉反应)、金属有机框架的形成(ZIF)和催化偶联反应(格拉泽反应),证明了原位拉曼光谱在基于RAM的合成中的稳健性和通用性。