Naslov
Toward Mechanistic Understanding of Mechanochemical Reactions Using Real-Time In Situ Monitoring

Autori
Lukin, Stipe ; Germann, Luzia S. ; Friščić, Tomislav ; Halasz, Ivan

Izvornik
Accounts of chemical research (0001-4842) 55 (2022), 9; 1262-1277

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, pregledni rad, znanstveni

Ključne riječi
Raman spectroscopy ; Diffraction ; Chemical reactions ; Materials ; Mechanism

Sažetak
The past two decades have witnessed a rapid emergence of interest in mechanochemistry–chemical and materials reactivity achieved or sustained by the action of mechanical force–which has led to application of mechanochemistry to almost all areas of modern chemical and materials synthesis: from organic, inorganic, and organometallic chemistry to enzymatic reactions, formation of metal–organic frameworks, hybrid perovskites, and nanoparticle-based materials. The recent success of mechanochemistry by ball milling has also raised questions about the underlying mechanisms and has led to the realization that the rational development and effective harnessing of mechanochemical reactivity for cleaner and more efficient chemical manufacturing will critically depend on establishing a mechanistic understanding of these reactions. Despite their long history, the development of such a knowledge framework for mechanochemical reactions is still incomplete. This is in part due to the, until recently, unsurmountable challenge of directly observing transformations taking place in a rapidly oscillating or rotating milling vessel, with the sample being under the continuous impact of milling media. A transformative change in mechanistic studies of milling reactions was recently introduced through the first two methodologies for real-time in situ monitoring based on synchrotron powder X-ray diffraction and Raman spectroscopy. Introduced in 2013 and 2014, the two new techniques have inspired a period of tremendous method development, resulting also in new techniques for mechanistic mechanochemical studies that are based on temperature and/or pressure monitoring, extended X-ray fine structure (EXAFS), and, latest, nuclear magnetic resonance (NMR) spectroscopy. The new technologies available for real-time monitoring have now inspired the development of experimental strategies and advanced data analysis approaches for the identification and quantification of short-lived reaction intermediates, the development of new mechanistic models, as well as the emergence of more complex monitoring methodologies based on two or three simultaneous monitoring approaches. The use of these new opportunities has, in less than a decade, enabled the first real-time observations of mechanochemical reaction kinetics and the first studies of how the presence of additives, or other means of modifying the mechanochemical reaction, influence reaction rates and pathways. These studies have revealed multistep reaction mechanisms, enabled the identification of autocatalysis, as well as identified molecules and materials that have previously not been known or have even been considered not possible to synthesize through conventional approaches. Mechanistic studies through in situ powder X-ray diffraction (PXRD) and Raman spectroscopy have highlighted the formation of supramolecular complexes (for example, cocrystals) as critical intermediates in organic and metal–organic synthesis and have also been combined with isotope labeling strategies to provide a deeper insight into mechanochemical reaction mechanisms and atomic and molecular dynamics under milling conditions. This Account provides an overview of this exciting, rapidly evolving field by presenting the development and concepts behind the new methodologies for real-time in situ monitoring of mechanochemical reactions, outlining key advances in mechanistic understanding of mechanochemistry, and presenting selected studies important for pushing forward the boundaries of measurement techniques, data analysis, and mapping of reaction mechanisms.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA