Dispersive x-ray absorption spectroscopy for time-resolved in situ monitoring of mechanochemical reactions

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 & SIM;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. (C) 2022 Author(s).All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY)license (http://creativecommons.org/licenses/by/4.0/).

Automated summary

This study demonstrates the use of time-resolved in situ X-ray absorption spectroscopy (TRIS-XAS) for studying mechanochemical synthesis and reaction kinetics. The improved TRIS-DXAS method provides unprecedented detail and time resolution for monitoring the electronic structure of solids during reactions.