Transition metal oxide complexes as molecular catalysts for selective methane to methanol transformation: any prospects or time to retire?

• Published in: Physical chemistry chemical physics : PCCP 2023-02, Vol.25 (7), p.5313-5326
• Main Authors: Claveau, Emily E, Sader, Safaa, Jackson, Benjamin A, Khan, Shahriar N, Miliordos, Evangelos
• Format: Article
• Language: English
• Subjects: Catalysts; Computational chemistry; Conversion; Electronic structure; Hydrogen bonds; Machine learning; Metal oxides; Methane; Methanol; Oxidation; Oxidizing agents; Oxygen; Selectivity; Transition metal oxides
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp05480a

Transition metal oxides have been extensively used in the literature for the conversion of methane to methanol. Despite the progress made over the past decades, no method with satisfactory performance or economic viability has been detected. The main bottleneck is that the produced methanol oxidizes further due to its weaker C-H bond than that of methane. Every improvement in the efficiency of a catalyst to activate methane leads to reduction of the selectivity towards methanol. Is it therefore prudent to keep studying (both theoretically and experimentally) metal oxides as catalysts for the quantitative conversion of methane to methanol? This perspective focuses on molecular metal oxide complexes and suggests strategies to bypass the current bottlenecks with higher weight on the computational chemistry side. We first discuss the electronic structure of metal oxides, followed by assessing the role of the ligands in the reactivity of the catalysts. For better selectivity, we propose that metal oxide anionic complexes should be explored further, while hydrophylic cavities in the vicinity of the metal oxide can perturb the transition-state structure for methanol increasing appreciably the activation barrier for methanol. We also emphasize that computational studies should target the activation reaction of methanol (and not only methane), the study of complete catalytic cycles (including the recombination and oxidation steps), and the use of molecular oxygen as an oxidant. The titled chemical conversion is an excellent challenge for theory and we believe that computational studies should lead the field in the future. It is finally shown that bottom-up approaches offer a systematic way for exploration of the chemical space and should still be applied in parallel with the recently popular machine learning techniques. To answer the question of the title, we believe that metal oxides should still be considered provided that we change our focus and perform more systematic investigations on the activation of methanol. The performance of transition metal oxides for converting methane to methanol is assessed and two kinds of molecular catalysts are proposed to improve their selectivity: metal oxides with hydrophilic ligands or metal oxide anionic complexes.