Charge Transfer Stabilization of Late Transition Metal Oxide Nanoparticles on a Layered Niobate Support

Interfacial interactions between late transition metal/metal oxide nanoparticles and oxide supports impact catalytic activity and stability. Here, we report the use of isothermal titration calorimetry (ITC), electron microscopy and density functional theory (DFT) to explore periodic trends in the heats of nanoparticle–support interactions for late transition metal and metal oxide nanoparticles on layered niobate and silicate supports. Data for Co­(OH)₂, hydroxyiridate-capped IrO_<i>x</i>·<i>n</i>H₂O, Ni­(OH)₂, CuO, and Ag₂O nanoparticles were added to previously reported data for Rh­(OH)₃ grown on nanosheets of TBA_0.24H_0.76Ca₂Nb₃O₁₀ and a layered silicate. ITC measurements showed stronger bonding energies in the order Ag < Cu ≈ Ni ≈ Co < Rh < Ir on the niobate support, as expected from trends in M–O bond energies. Nanoparticles with exothermic heats of interaction were stabilized against sintering. In contrast, ITC measurements showed endothermic interactions of Cu, Ni, and Rh oxide/hydroxide nanoparticles with the silicate and poor resistance to sintering. These trends in interfacial energies were corroborated by DFT calculations using single-atom and four-atom cluster models of metal/metal oxide nanoparticles. Density of states and charge density difference calculations reveal that strongly bonded metals (Rh, Ir) transfer d-electron density from the adsorbed cluster to niobium atoms in the support; this mixing is absent in weakly binding metals, such as Ag and Au, and in all metals on the layered silicate support. The large differences between the behavior of nanoparticles on niobate and silicate supports highlight the importance of d-orbital interactions between the nanoparticle and support in controlling the nanoparticles’ stability