Abstract
This study presents a single-site microkinetic model for methanol synthesis by CO(2) hydrogenation over intermetallic Pd(2)Ga/SiO(2). A reaction path analysis (RPA) combining theoretical results and realistic catalyst surface reaction data is established to elucidate the reaction mechanism and kinetic models of CO(2) hydrogenation to methanol and CO. The RPA leads to the derivation of rate expressions for both reactions without presumptions about the most abundant reactive intermediate (MARI) and rate-determining step (rds). The formation of H(2)COOH* is found to be the rds (step 19) for methanol synthesis via the formate pathway, with CO(2) and H-atoms adsorbed on intermetallic sites as the MARIs. The derived kinetic model is corroborated with experimental data acquired under different reaction conditions, using a lab-scale fixed-bed reactor and Pd(2)Ga/SiO(2) nanoparticles prepared by incipient wetness impregnation. The excellent agreement between the experimental data and the kinetic model (R (2) = 0.99) substantiates the proposed mechanism with an activation energy of 61.52 kJ mol(-1) for methanol synthesis. The reported catalyst exhibits high selectivity to methanol (96%) at 1 bar, 150 °C, and H(2)/CO(2) ratio of 3:1. These findings provide critical insights to optimize catalysts and processes targeting CO(2) hydrogenation at atmospheric pressure and low temperatures for on-demand energy production.