(679f) Adhesion Energy Trends for Catalytic Metal Nanoparticles on Carbon and Oxide Supports with Applications in Predicting Performance

Late transition metal nanoparticles supported on high surface area materials catalysts are essential in many industrial chemical production processes and promising for new and emerging applications. Understanding fundamental structure-function relationships of nanoparticle catalysts on support materials informs efficient catalyst design and provides benchmarks for computational predictions. We directly measure metal adsorption energies and metal atom chemical potential on model catalyst supports via single crystal adsorption calorimetry (SCAC) to gain information about the interactions between the catalyst supports and metal nanoparticles. Previous metal/support systems studied in this way have provided insights into the fundamental behavior of catalysts and correlations of catalyst behavior with metal chemical potential. Metal/support adhesion energies allow estimating this chemical potential versus particle size on different supports, and thus provide information on reactivity and sintering resistance of metal nanoparticles. Linear correlations between the oxophilicity of metals and their adhesion energy to MgO(100) and CeO₂(111) have been demonstrated. The adhesion energy of Ag to rutile-TiO₂(100) has been previously measured. Here, we expand upon the existing oxide adhesion energy trends with new SCAC measurements of Cu on rutile-TiO₂(100). The new oxide correlation gives insight into the relationship between the oxide support and the adhesion energy, to predict adhesion energies across oxide surfaces. We also extend adhesion energy measurements to carbon surfaces with new SCAC results for Pd nanoparticles on single-layer graphene supported on Ni(111). Combined with previous measurements of Ni and Ag on graphene/Ni(111), we find that these adhesion energies to graphene scale linearly with metal carbophilicity, which we define as the DFT bond energy of one C atom to the (111) face of that metal. This trend suggests the adhesion energies of other late transition metals to graphene films on Ni(111).