Reactive gas environment induced structural modification of noble-transition metal alloy nanoparticles.

Noble-transition metal (noble=Pt,Au; transition=Co,Ni,Cu) alloy particles with sizes of about 5 nm have been studied by in situ high-energy x-ray diffraction while subjected to oxidizing (O(2)) and reducing (H(2)) gas atmospheres at elevated temperatures. The different gas atmospheres do not affect substantially the random alloy, face-centered-cubic structure type of the particles but do affect the way the metal atoms pack together. In an O(2) atmosphere, atoms get extra separated from each other, whereas, in an H(2) atmosphere, they come closer together. The effect is substantial, amounting to 0.1 Å difference in the first neighbor atomic distances, and concurs with a dramatic change of the particle catalytic properties. It is argued that such reactive gas induced "expansion shrinking" is a common phenomenon that may be employed for the engineering of "smart" nanoparticles responding advantageously to envisaged gas environments.