Conversion of Carbon Monoxide into Methanol on Alumina-Supported Cobalt Catalyst: Role of the Support and Reaction Mechanism—A Theoretical Study

Density functional theory (DFT) was used to calculate the step-by-step hydrogenation of carbon monoxide (CO) to form methanol over a Co4 cluster/Al2O3 surface. A three-dimensional Co4 tetrahedral structure was selected to explore its interaction with the supporting Al2O3 (104) surface. Co4 chemically reacted with Al2O3 to form a new chemical system. The calculated results show that Al2O3 support has strengthened the Co4 catalyst during the reaction since the formation of the Co–O bond. Loading Co4 on the Al2O3 surface increases CO adsorption ability but decreases the dissociation ability of C–O to produce hydrocarbons. As such, CH3OH formation becomes more favorable both kinetically and thermodynamically on Co4/Al2O3. In CO hydrogenation, methanol was synthesized through a CO reaction with hydrogen via either an Eley–Rideal or Langmuir–Hinshelwood pathway to form the intermediates C*-O-H, H-C*-OH, H2-C*-OH, and finally the hydrogenation of H2-C*-OH to methanol with both hydrogenation steps forming C*-OH and final product as rate-limiting. These results showed that the interaction between Co, Al2O3 and H2 pressure can change the pathway of CO hydrogenation on Co/Al2O3 and it may, therefore, influence distribution of the final products.