Identifying Descriptors for Promoted Rhodium-Based Catalysts for Higher Alcohol Synthesis via Machine Learning

Rhodium-based catalysts offer remarkable selectivities toward higher alcohols, specifically ethanol, via syngas conversion. However, the addition of metal promoters is required to increase reactivity, augmenting the complexity of the system. Herein, we present an interpretable machine learning (ML) approach to predict and rationalize the performance of Rh-Mn-P/SiO₂ catalysts (P = 19 promoters) using the open-source dataset on Rh-catalyzed higher alcohol synthesis (HAS) from Pacific Northwest National Laboratory (PNNL). A random forest model trained on this dataset comprising 19 alkali, transition, post-transition metals, and metalloid promoters, using catalytic descriptors and reaction conditions, predicts the higher alcohols space-time yield (STY_HA) with an accuracy of R ² = 0.76. The promoter's cohesive energy and alloy formation energy with Rh are revealed as significant descriptors during posterior feature-importance analysis. Their interplay is captured as a dimensionless property, coined promoter affinity index (PAI), which exhibits volcano correlations for space-time yield. Based on this descriptor, we develop guidelines for the rational selection of promoters in designing improved Rh-Mn-P/SiO₂ catalysts. This study highlights ML as a tool for computational screening and performance prediction of unseen catalysts and simultaneously draws insights into the property-performance relations of complex catalytic systems.