Water and Cu+ Synergy in Selective CO2 Hydrogenation to Methanol over Cu-MgO-Al2O3 Catalysts.

The CO2 hydrogenation reaction to produce methanol holds great significance as it contributes to achieving a CO2-neutral economy. Previous research identified isolated Cu+ species doping the oxide surface of a Cu-MgO-Al2O3-mixed oxide derived from a hydrotalcite precursor as the active site in CO2 hydrogenation, stabilizing monodentate formate species as a crucial intermediate in methanol synthesis. In this work, we present a molecular-level understanding of how surface water and hydroxyl groups play a crucial role in facilitating spontaneous CO2 activation at Cu+ sites and the formation of monodentate formate species. Computational evidence has been experimentally validated by comparing the catalytic performance of the Cu-MgO-Al2O3 catalyst with hydroxyl groups against that of its hydrophobic counterpart, where hydroxyl groups are blocked using an esterification method. Our work highlights the synergistic effect between doped Cu+ ions and adjacent hydroxyl groups, both of which serve as key parameters in regulating methanol production via CO2 hydrogenation. By elucidating the specific roles of these components, we contribute to advancing our understanding of the underlying mechanisms and provide valuable insights for optimizing methanol synthesis processes.

From Methane to Methanol: Pd-iC-CeO2 Catalysts Engineered for High Selectivity via Mechanochemical Synthesis.

In the pursuit of selective conversion of methane directly to methanol in the liquid-phase, a common challenge is the concurrent formation of undesirable liquid oxygenates or combustion byproducts. However, we demonstrate that monometallic Pd-CeO2 catalysts, modified by carbon, created by a simple mechanochemical synthesis method exhibit 100% selectivity toward methanol at 75 °C, using hydrogen peroxide as oxidizing agent. The solvent free synthesis yields a distinctive Pd-iC-CeO2 interface, where interfacial carbon (iC) modulates metal-oxide interactions and facilitates tandem methane activation and peroxide decomposition, thus resulting in an exclusive methanol selectivity of 100% with a yield of 117 µmol/gcat at 75 °C. Notably, solvent interactions of H2O2 (aq) were found to be critical for methanol selectivity through a density functional theory (DFT)-simulated Eley-Rideal-like mechanism. This mechanism uniquely enables the direct conversion of methane into methanol via a solid-liquid-gas process.