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Constructing and interpreting volcano plots and activity maps to navigate homogeneous catalyst landscapes

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Abstract

Volcano plots and activity maps are powerful tools for studying homogeneous catalysis. Once constructed, they can be used to estimate and predict the performance of a catalyst from one or more descriptor variables. The relevance and utility of these tools has been demonstrated in several areas of catalysis, with recent applications to homogeneous catalysts having been pioneered by our research group. Both volcano plots and activity maps are built from linear free energy scaling relationships that connect the value of a descriptor variable(s) with the relative energies of other catalytic cycle intermediates/transition states. These relationships must be both constructed and postprocessed appropriately to obtain the resulting plots/maps; this process requires careful execution to obtain meaningful results. In this protocol, we provide a step-by-step guide to building volcano plots and activity maps using curated reaction profile data. The reaction profile data are obtained using density functional theory computations to model the catalytic cycle. In addition, we provide volcanic, a Python code that automates the steps of the process following data acquisition. Unlike the computation of individual reaction energy profiles, our tools lead to a holistic view of homogeneous catalyst performance that can be broadly applied for both explanatory and screening purposes.

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Fig. 1: General workflow of the procedure.
Fig. 2: Schematic outline of the volcano plot construction process.
Fig. 3: Examples of catalytic processes that have been studied using different variants of the volcano plots.
Fig. 4: Volcano plot study of CO2 hydrogenation with transition metal pincer complexes.
Fig. 5: Volcano plot and activity map study of C–C cross-coupling reactions.

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Data availability

All data to reproduce all the figures of this work are available at https://github.com/lcmd-epfl/volcanic, as well as instructions to generate such plots using the volcanic package.

Code availability

The volcanic package is available at https://github.com/lcmd-epfl/volcanic. Supplementary Methods detail the manual procedure for the application highlighted in Fig. 4.

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Acknowledgements

The authors are grateful to the EPFL for financial support and computational resources. This publication was created as part of NCCR Catalysis (grant number 180544), a National Centre for Competence in Research funded by the Swiss National Science Foundation (financial support of R.L.). The Swiss National Science Foundation (grant no. 200020-175496) is acknowledged for financial support of S.D. P. Steinbach is acknowledged for his contribution to one of the volcanic modules.

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Authors and Affiliations

  1. Laboratory for Computational Molecular Design (LCMD), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Rubén Laplaza, Shubhajit Das, Matthew D. Wodrich & Clémence Corminboeuf

  2. National Center for Competence in Research-Catalysis (NCCR-Catalysis), École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

    Rubén Laplaza, Matthew D. Wodrich & Clémence Corminboeuf

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  1. Rubén Laplaza
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  2. Shubhajit Das
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  4. Clémence Corminboeuf
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All authors contributed to the conceptualization, elaboration of the content and writing of the manuscript.

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Correspondence to Clémence Corminboeuf.

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Nature Protocols thanks Xin Hong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Related Links

Key references using this protocol

Busch, M. et. al. Chem. Sci. 6, 6754–6761 (2015): https://doi.org/10.1039/C5SC02910D

Wodrich, M. D. et. al. Chem. Sci. 7, 5723–5735 (2016): https://doi.org/10.1039/C6SC01660J

Busch, M., et. al. ACS Catal. 7, 5643–5653 (2017): https://doi.org/10.1021/acscatal.7b01415

Wodrich, M. D. et. al. ChemCatChem 10, 1586–1591 (2018): https://doi.org/10.1002/cctc.201701709

Wodrich, M. D. et. al. ACS Catal. 9, 5716–5725 (2019): https://doi.org/10.1021/acscatal.9b00717

Key data used in this protocol

Wodrich, M. D. et. al. Chem. Sci. 7, 5723–5735 (2016): https://doi.org/10.1039/C6SC01660J

Busch, M., et. al. ACS Catal. 7, 5643–5653 (2017): https://doi.org/10.1021/acscatal.7b01415

Cordova, M. et. al. ACS Catal. 10, 7021–7031 (2020): https://doi.org/10.1021/acscatal.0c00774

Das, S. et. al. Top. Catal. 65, 289–295 (2022): https://doi.org/10.1007/s11244-021-01480-7

Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figs. 1–5 and Supplementary Table 1.

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Laplaza, R., Das, S., Wodrich, M.D. et al. Constructing and interpreting volcano plots and activity maps to navigate homogeneous catalyst landscapes. Nat Protoc 17, 2550–2569 (2022). https://doi.org/10.1038/s41596-022-00726-2

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