The Genesis of Molecular Volcano Plots

For the past two decades, linear free energy scaling relationships and volcano plots have seen frequent use as computational tools that aid in understanding and predicting the catalytic behavior of heterogeneous and electrocatalysts. Based on Sabatier's principle, which states that a catalyst should bind a substrate neither too strongly nor too weakly, volcano plots provide an estimate of catalytic performance (e.g., overpotential, catalytic cycle thermodynamics/kinetics, etc.) through knowledge of a descriptor variable. By the use of linear free energy scaling relationships, the value of this descriptor is employed to estimate the relative energies of other catalytic cycle intermediates/transition states. Postprocessing of these relationships leads to a volcano curve that reveals the anticipated performance of each catalyst, with the best species appearing on or near the peak or plateau. While the origin of volcanoes is undoubtedly rooted in examining heterogeneously catalyzed reactions, only recently has this concept been transferred to the realm of homogeneous catalysis. This Account summarizes the work done by our group in implementing and refining molecular volcano plots for use in analyzing and predicting the behavior of homogeneous catalysts. We begin by taking the reader through the initial proof-of-principle study that transferred the model from heterogeneous to homogeneous catalysis by examining thermodynamic aspects of a Suzuki-Miyaura cross-coupling reaction. By establishing linear free energy scaling relationships and reproducing the volcano shape, we definitively showed that volcano plots are also valid for homogeneous systems. On the basis of this key finding, we further illustrate how unified pictures of C-C cross-coupling thermodynamics were created using three-dimensional molecular volcanoes. The second section highlights an important transformation from thermodynamic to kinetic volcanoes by using the descriptor variable to directly estimate transition state barriers. Taking this idea further, we demonstrate how volcanoes can be used to directly predict an experimental observable, the turnover frequency. Discussion is also provided on how different flavors of molecular volcanoes can be used to analyze aspects of homogeneous catalysis of interest to experimentalists, such as determining the product selectivity and probing the substrate scope. The third section focuses on incorporating machine learning approaches into molecular volcanoes and invoking big-data-type approaches in the analysis of catalytic behavior. Specifically, we illustrate how machine learning can be used to predict the value of the descriptor variable, which facilitates nearly instantaneous screening of thousands of catalysts. With the large amount of data created from the machine learning/volcano plot tandem, we show how the resulting database can be mined to garner an enhanced understanding of catalytic processes. Emphasis is also placed on the latest generation of augmented volcano plots, which differ fundamentally from earlier volcanoes by elimination of the use of linear free energy scaling relationships and by assessment of the similarity of the complete catalytic cycle energy profile to that for an ideal reference species that is used to discriminate catalytic performance. We conclude by examining a handful of applications of molecular volcano plots to interesting problems in homogeneous catalysis and offering thoughts on the future prospects and uses of this new set of tools.

Automated summary

Volcano plots are computational tools widely used for predicting catalytic behavior in heterogeneous and electrocatalysts, estimating catalytic performance through descriptor variables. Recent studies have shown the applicability of volcano plots in homogeneous catalysis, revealing the potential of these plots to analyze and predict catalyst behavior. The integration of machine learning approaches into molecular volcanoes and the development of augmented volcano plots represent the future direction of catalysis analysis and prediction.