Computational Discovery of Stable Metal-Organic Frameworks for Methane-to-Methanol Catalysis.

The challenge of direct partial oxidation of methane to methanol has motivated the targeted search of metal-organic frameworks (MOFs) as a promising class of materials for this transformation because of their site-isolated metals with tunable ligand environments. Thousands of MOFs have been synthesized, yet relatively few have been screened for their promise in methane conversion. We developed a high-throughput virtual screening workflow that identifies MOFs from a diverse space of experimental MOFs that have not been studied for catalysis, yet are thermally stable, synthesizable, and have promising unsaturated metal sites for C-H activation via a terminal metal-oxo species. We carried out density functional theory calculations of the radical rebound mechanism for methane-to-methanol conversion on models of the secondary building units (SBUs) from 87 selected MOFs. While we showed that oxo formation favorability decreases with increasing 3d filling, consistent with prior work, previously observed scaling relations between oxo formation and hydrogen atom transfer (HAT) are disrupted by the greater diversity in our MOF set. Accordingly, we focused on Mn MOFs, which favor oxo intermediates without disfavoring HAT or leading to high methanol release energies─a key feature for methane hydroxylation activity. We identified three Mn MOFs comprising unsaturated Mn centers bound to weak-field carboxylate ligands in planar or bent geometries with promising methane-to-methanol kinetics and thermodynamics. The energetic spans of these MOFs are indicative of promising turnover frequencies for methane to methanol that warrant further experimental catalytic studies.

Machine Learning Models Predict Calculation Outcomes with the Transferability Necessary for Computational Catalysis.

Virtual high-throughput screening (VHTS) and machine learning (ML) have greatly accelerated the design of single-site transition-metal catalysts. VHTS of catalysts, however, is often accompanied with a high calculation failure rate and wasted computational resources due to the difficulty of simultaneously converging all mechanistically relevant reactive intermediates to expected geometries and electronic states. We demonstrate a dynamic classifier approach, i.e., a convolutional neural network that monitors geometry optimizations on the fly, and exploit its good performance and transferability in identifying geometry optimization failures for catalyst design. We show that the dynamic classifier performs well on all reactive intermediates in the representative catalytic cycle of the radical rebound mechanism for the conversion of methane to methanol despite being trained on only one reactive intermediate. The dynamic classifier also generalizes to chemically distinct intermediates and metal centers absent from the training data without loss of accuracy or model confidence. We rationalize this superior model transferability as arising from the use of electronic structure and geometric information generated on-the-fly from density functional theory calculations and the convolutional layer in the dynamic classifier. When used in combination with uncertainty quantification, the dynamic classifier saves more than half of the computational resources that would have been wasted on unsuccessful calculations for all reactive intermediates being considered.