Catalytic resonance theory for parametric uncertainty of programmable catalysis

Microkinetic models are useful tools for screening catalytic materials; however, errors in their input parameters can lead to significant uncertainty in model predictions of catalyst performance. Here, in this work, we investigate the impact of linear scaling and Brønsted-Evans-Polanyi relation parametric uncertainty on microkinetic predictions of programmable-catalyst performance. Two case studies are considered: a generic A-to-B prototype reaction and the oxygen evolution reaction (OER). The results show that error-unaware models can accurately predict trends and, for the prototype reaction, values of optimal waveform parameters. The specific model parameters driving output uncertainty are identified via variance-based global sensitivity analysis. However, predictions of dynamic rate enhancement can decrease when uncertainty is propagated into the models. In both cases, we identify operating conditions where the programmable catalyst achieves a rate enhancement of at least one order of magnitude despite parametric uncertainty in the model, supporting programmable catalysis as a viable strategy for exceeding the Sabatier limit.. Authors: Gathmann, Sallye R. [Univ. of Minnesota, Minneapolis, MN (United States)]; Jung, Seongjoo; Dauenhauer, Paul J. [Univ. of Minnesota, Minneapolis, MN (United States)] (ORCID:0000000158101953). DOE Contract: SC0023464. Subjects: Monte Carlo; catalysis; dynamic; programmable; uncertainty