In situ and real-time monitoring of mechanochemical milling reactions using synchrotron X-ray diffraction

Abstract

We describe the only currently available protocol for in situ, real-time monitoring of mechanochemical reactions and intermediates by X-ray powder diffraction. Although mechanochemical reactions (inducing transformations by mechanical forces such as grinding and milling) are normally performed in commercially available milling assemblies, such equipment does not permit direct reaction monitoring. We now describe the design and in-house modification of milling equipment that allows the reaction jars of the operating mill to be placed in the path of a high-energy (90 keV) synchrotron X-ray beam while the reaction is taking place. Resulting data are analyzed using conventional software, such as TOPAS. Reaction intermediates and products are identified using the Cambridge Structural Database or Inorganic Crystal Structure Database. Reactions are analyzed by fitting the time-resolved diffractograms using structureless Pawley refinement for crystalline phases that are not fully structurally characterized (such as porous frameworks with disordered guests), or the Rietveld method for solids with fully determined crystal structures (metal oxides, coordination polymers).

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Milling equipment for in situ X-ray diffraction measurements.
Figure 2: Chemical reaction and experimental setup.
Figure 3: Experiment preparation.
Figure 4: Outside control of mill operation.
Figure 5: Data processing.
Figure 6: Data presentation and quantitative analysis.
Figure 7: Qualitative identification of products using Mercury.

References

  1. 1

    James, S.L. et al. Mechanochemistry: opportunities for new and cleaner synthesis. Chem. Soc. Rev. 41, 413–447 (2012).

  2. 2

    Takacs, L. The historical development of mechanochemistry. Chem. Soc. Rev. http://dx.doi.org/10.1039/C2CS35442J (7 February 2013).

  3. 3

    Ling, A.R. & Baker, J.L. Halogen derivatives of quinone. Part III. Derivatives of quinhydrone. J. Chem. Soc. 63, 1314–1327 (1893).

  4. 4

    Wiggins, K.M., Brantely, J.N. & Bielawski, C.W. Methods for activating and characterizing mechanically responsive polymers. Chem. Soc. Rev. http://dx.doi.org/10.1039/C3CS35493H (7 February 2013).

  5. 5

    Beyer, M.K. & Clausen-Schaumann, H. Mechanochemistry: the mechanical activation of covalent bonds. Chem. Rev. 105, 2921–2948 (2005).

  6. 6

    Stolle, A., Szuppa, T., Leonhardt, S.E.S. & Ondruschka, B. Ball milling in organic synthesis: solutions and challenges. Chem. Soc. Rev. 40, 2317–2329 (2011).

  7. 7

    Belcher, W.J., Longstaff, C.A., Neckening, M.R. & Steed, J.W. Channel-containing 1D coordination polymers based on a linear dimetallic spacer. Chem. Commun. 2002, 1602–1603 (2002).

  8. 8

    Lazuen Garay, A., Pichon, A. & James, S.L. Solvent-free synthesis of metal complexes. Chem. Soc. Rev. 36, 846–855 (2007).

  9. 9

    Rodríguez, B., Bruckmann, A., Rantanen, T. & Bolm, C. Solvent-free carbon-carbon bond formations in ball mills. Adv. Synth. Catal. 349, 2213–2233 (2007).

  10. 10

    Belenguer, A.M., Friščić, T., Day, G.M. & Sanders, J.K.M. Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis. Chem. Sci. 3, 696–700 (2011).

  11. 11

    Užarević, K. et al. Dynamic molecular recognition in solid state for separating mixtures of isomeric dicarboxylic acids. Angew. Chem. Int. Ed. 52, 5504–5508 (2013).

  12. 12

    Urakaev, F.Kh. & Boldyrev, V.V. Mechanism and kinetics of mechanochemical processes in comminuting devices 2. Applications of the theory. Experiment. Powder Technol. 107, 197–206 (2000).

  13. 13

    Takacs, L. Self-sustaining reactions induced by ball milling. Prog. Mater. Sci. 47, 355–414 (2002).

  14. 14

    Friščić, T. et al. Real-time and in situ monitoring of mechanochemical milling reactions. Nat. Chem. 5, 66–73 (2013).

  15. 15

    Burmeister, C.F. & Kwade, A. Process engineering with planetary ball mills. Chem. Soc. Rev. http://dx.doi.org/10.1039/C3CS35455E (7 February 2013).

  16. 16

    Friščić, T., Halasz, I., Štrukil, V., Eckert-Maksić, M. & Dinnebier, R.E. Clean and efficient synthesis using mechanochemistry: coordination polymers, metal-organic frameworks and metallodrugs. Croat. Chem. Acta 85, 367–378 (2012).

  17. 17

    Friščić, T. Supramolecular concepts and new techniques in mechanochemistry: cocrystals, cages, rotaxanes, open metal-organic frameworks. Chem. Soc. Rev. 41, 3493–3510 (2012).

  18. 18

    Friščić, T. & Jones, W. Recent advances in understanding the mechanism of cocrystal formation via grinding. Cryst. Growth Des. 9, 1621–1637 (2009).

  19. 19

    Bowmaker, G.A. Solvent-assisted mechanochemistry. Chem. Commun. 49, 334–348 (2013).

  20. 20

    Braga, D. et al. Mechanochemical preparation of molecular and supramolecular organometallic materials and coordination networks. Dalton Trans. 1249–1263 (2006).

  21. 21

    Friščić, T. et al. Ion- and liquid-assisted grinding: improved mechanochemical synthesis of metal-organic frameworks reveals salt inclusion and anion templating. Angew. Chem. Int. Ed. 49, 712–715 (2010).

  22. 22

    Kuroda, R., Yoshida, J., Nakamura, A. & Nishikiori, S.-i. Annealing assisted mechanochemical syntheses of transition-metal coordination compounds and co-crystal formation. CrystEngComm 11, 427–432 (2009).

  23. 23

    Hsueh, S.-Y., Cheng, K.-W., Lai, C.-C. & Chiu, S.-H. Efficient solvent-free syntheses of [2]- and [4]Rotaxanes. Angew. Chem. Int. Ed. 47, 4436–4439 (2007).

  24. 24

    Friščić, T. New opportunities for materials synthesis using mechanochemistry. J. Mat. Chem. 20, 7599–7605 (2010).

  25. 25

    Trask, A.V., Motherwell, W.D.S. & Jones, W. Solvent-drop grinding: green polymorph control of cocrystallisation. Chem. Commun. 890–891 (2004).

  26. 26

    Friščić, T., Childs, S.L., Rizvi, S.A.A. & Jones, W. The role of solvent in mechanochemical and sonochemical cocrystal formation: a solubility-based approach for predicting cocrystallisation outcome. CrystEngComm 11, 418–426 (2009).

  27. 27

    Beldon, P.J. et al. Rapid room-temperature synthesis of zeolitic imidazolate frameworks by using mechanochemistry. Angew. Chem. Int. Ed. 49, 9640–9643 (2010).

  28. 28

    Zhang, J.-P., Zhang, Y.-B., Lin, J.-B. & Chen, X.-M. Metal azolate frameworks: from crystal engineering to functional materials. Chem. Rev. 112, 1001–1033 (2012).

  29. 29

    Šepelák, V., Bégin-Colin, S. & Le Caër, G. Transformations in oxides induced by high-energy ball-milling. Dalton Trans. 41, 11927–11948 (2012).

  30. 30

    Ravnsbæk, D.B., Sørensen, L.H., Filinchuk, Y., Besenbacher, F. & Jensen, T.R. Screening of metal borohydrides by mechanochemistry and diffraction. Angew. Chem. Int. Ed. 51, 3582–3586 (2012).

  31. 31

    Biswal, B.P. et al. Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks. J. Am. Chem. Soc. 135, 5328–5331 (2013).

  32. 32

    Içli, B. et al. Synthesis of molecular nanostructures by multicomponent condensation reactions in a ball mill. J. Am. Chem. Soc. 131, 3154–3155 (2009).

  33. 33

    Cliffe, M.J., Mottilo, C., Stein, R.S., Bučar, D.-K. & Friščić, T. Accelerated aging: a low energy, solvent-free alternative to solvothermal and mechanochemical synthesis of metal–organic frameworks. Chem. Sci. 3, 2495–2500 (2012).

Download references

Acknowledgements

We acknowledge financial support from the Herchel Smith Fund; the British Council/The German Academic Exchange Service (DAAD) (grant no. 1377); the ESRF; NanoDTC, the University of Cambridge; the Ministry of Science, Education and Sports of the Republic of Croatia (grant no. 098-0982904-2953) and EPSRC (A.M.B.); as well as from a research fellowship (T.F.) and a doctoral fellowship (P.J.B.). McGill University, the Fonds Québécois de la Recherche sur la Nature et les Technologies (FRQNT) Centre for Green Chemistry and Catalysis, a FRQNT Nouveaux Chercheurs grant and a Canadian Natural Sciences and Engineering Research Council (NSERC) Discovery grant are acknowledged for support (T.F.). We thank A.K. Cheetham for comments, W. Jones for support in acquiring the instrumentation and J.K.M. Sanders for support. The assistance of A. Kovač and V. Dunjko with graphics preparation is acknowledged. N. Pitt is acknowledged for photography.

Author information

Affiliations

Authors

Contributions

The manuscript was composed and research was performed by I.H., S.A.J.K., P.J.B., A.M.B., F.A., V.H. and T.F. Detailed designs for mill modification were provided by R.C.N. Research was organized by T.F., I.H. and R.E.D. Manuscript preparation and submission were organized by T.F.

Corresponding author

Correspondence to Tomislav Friščić.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Manual

Technical drawings of the mill extension and milling jar. (PDF 566 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Halasz, I., Kimber, S., Beldon, P. et al. In situ and real-time monitoring of mechanochemical milling reactions using synchrotron X-ray diffraction. Nat Protoc 8, 1718–1729 (2013). https://doi.org/10.1038/nprot.2013.100

Download citation

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.