Abstract
Orders in catalyst greater than one can be attributed to several different reaction mechanisms. Differentiating among these possibilities requires careful analysis of their rate laws, rational experiment design and accurate measurement of the progress of the reactions. We have compiled the most popular mechanisms proposed for reactions with an order in catalyst greater than one and derived their steady-state rate laws. We have analysed the rate laws and proposed experiments to discern between mechanisms. Finally, we have examined 100 case studies that showcase good practices to propose robust mechanisms and to avoid common pitfalls.
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Fitting results are available in the Supplementary Information.
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09 January 2023
In the version of this article initially published, the Supplementary information, “Fitting results” were missing and are now included in the online version of the article.
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Acknowledgements
We thank many colleagues for useful and inspiring discussions over the years, especially Prof. Donna Blackmond, Prof. Alan Armstrong, Prof. Igor Larrosa, Prof. Jason Hein and Dr. David Sale. We also thank all the authors of the case studies analysed in the Supplementary Information for the data reported. We acknowledge funding from the EPSRC projects EP/S005315/1, EP/R513131/1 and EP/T030666/1.
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J.B. conceived the Review and wrote the manuscript. C.A.-F. and G.H. analysed the data and wrote the Supplementary Information.
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Alamillo-Ferrer, C., Hutchinson, G. & Burés, J. Mechanistic interpretation of orders in catalyst greater than one. Nat Rev Chem 7, 26–34 (2023). https://doi.org/10.1038/s41570-022-00447-w
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DOI: https://doi.org/10.1038/s41570-022-00447-w
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