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A new mechanism for reactivity of multiply twinned gold nanoparticlesresulting from their inherently strained structure provides a furtherexplanation of the surprising catalytic activity of small gold nanoparticles.Atomic defect structural studies of surface strains and quantitative analysisof atomic column displacements in the decahedral structure observed byaberration corrected transmission electron microscopy reveal an averageexpansion of surface nearest neighbor distances of 5.6 percent, with manystrained by more than 10 percent. Density functional theory calculations of theresulting modified gold d-band states predict significantly enhanced activityfor carbon monoxide oxidation. The new insights have important implications forthe applications of nanoparticles in chemical process technology, including forheterogeneous catalysis.

On the Structural Origin of the Catalytic Properties of Inherently Strained Ultrasmall Decahedral Gold Nanoparticles