Activating Molybdenum Carbide Nanoparticle Catalysts under Mild Conditions Using Thermally Labile Ligands

Transition-metal carbides are promising low-cost materials for various catalytic transformations due to their multifunctionality and noble-metal-like behavior. Nanostructuring transition-metal carbides offers advantages resulting from the large surface-area-to-volume ratios inherent in colloidal nanoparticle catalysts; however, a barrier for their utilization is removal of the long-chain aliphatic ligands on their surface to access active sites. Annealing procedures to remove these ligands require temperatures greater than the catalyst synthesis and catalytic reaction temperatures and may further result in coking or particle sintering that can reduce catalytic performance. One way to circumvent this problem is by replacing the long-chain aliphatic ligands with smaller ligands that can be easily removed through low-temperature thermolytic decomposition. Here, we present the exchange of native oleylamine ligands on colloidal alpha-MoC1-x nanoparticles for thermally labile tert-butylamine ligands. Analyses of the ligand exchange reaction by solution H-1 NMR spectroscopy, FT-IR spectroscopy, and thermogravimetric analysis-mass spectrometry (TGA-MS) confirm the displacement of 60% of the native oleylamine ligands for the thermally labile tert-butylamine, which can be removed with a mild activation step at 250 ?. Catalytic site densities were determined by carbon monoxide (CO) chemisorption, demonstrating that the mild thermal treatment at 250 ? activates ca. 25% of the total binding sites, while the native oleylamine-terminated MoC1-x nanoparticles showed no available surface binding sites after this low-temperature treatment. The mild pretreatment at 250 ? also shows distinctly different initial activities and postinduction period selectivities in the CO2 hydrogenation reaction for the ligand exchanged MoC1-x nanoparticle catalysts and the as-prepared material.