Manipulation of Pt-Ni Tetrahexahedral Nanoframes Using a Gaseous Etching Method

Nanosized Platinum (Pt) nanocrystals (NCs) have been extensively investigated in catalytic fields because of their high reactivity due to the unique electron structure. However, the rarity and the high cost of Pt limit its applications in industry. To reduce the usage of Pt in catalytic industry, research interests have been extended to Pt-based nanoalloys. Among various nanostructures, nanoframes (NFs) showed promising catalytic performance even with a lower metallic loading dose. Herein, we report a facile and robust method to transfer the Pt-Ni tetrahexahedral (THH) NCs into THH NFs in which carbon monoxide (CO) plays a role of the etching reagent. The driving force of the etching is a formation of gaseous metallic complex, Ni(CO)4, known as Mond Process, preferentially dealloying nickel atoms along <100> directions of the Pt-Ni THH NCs. It is determined that the resultant Pt-Ni THH NFs possess an open, stable and high-index preserved nanostructure, in which the outside atomic layers are composed of only Pt atoms with surface strains. Compared to a solution-based etching process, this approach requires less etching time and generates a well-defined structure. The associated thermal annealing operation also releases extra internal stress, making the NFs more stable with fewer surface defects. Such Pt-Ni THH NFs show interesting potentials in the improvement of stability and activity as advanced catalysts.