Tuning catalytic activity through electronic structure modification is a grand challenge in the field of heterogeneous catalysis. Recent synthetic advances have produced very small (≤ 2nm), ligand-protected, nanoparticles with quantized, molecule-like electronic structures. Such nanoparticles have shown high catalytic activity for a variety of reactions. The small size and molecule-like electronic structure of these nanoparticles allows the investigation of fundamental questions like: how will the inclusion of a few heteroatoms (dopants) impact the electronic structure and chemistry of the resulting mixed-metal nanoparticle.The inclusion of heteroatoms will likely occur at specific, energetically favorable locations, and the nanoparticle's electronic structure will likely experience unique perturbations. Here we show that the electronic structure and chemical reactivity of small Au nanoparticles can be controllably perturbed by incorporation of heteroatoms (dopants). Electronic structure perturbations were studied with density functional theory (DFT) and experimental techniques such as optical absorbance and luminescence spectroscopy, X-ray photoelectron spectroscopy, non-aqueous electrochemistry, and <i>in situ </i>spectroelectrochemistry. Composition-dependent chemical reactivity was studied using electrochemical techniques. These results provide a route to control the electronic structure and chemical reactivity of small nanoparticles, and they help further the concept of “rational” catalyst design.

Controlling the electronic structure and chemical reactivity of small nanoparticles through atomic composition

249th National Meeting (2015)

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