Synthesis of Pt-Rare Earth Metal Nanoalloys.

Chemical synthesis of platinum-rare earth metal (Pt-RE) nanoalloys, one of the most active catalysts for the oxygen reduction reaction, has been a formidable challenge, mainly due to the vastly different standard reduction potentials of the two metals and high oxophilicity of the latter. Here we report a universal chemical process to prepare Pt-RE nanoalloys with tunable compositions and particle sizes. Pt and RE metal ions from the most common hydrated metal salts are first atomically embedded into an in situ formed C-N network, yielding a stable compound insensitive to O2 and H2O. The Pt-RE nanoalloys are subsequently obtained by heating the compound under a mild reducing atmosphere (e.g., 3.3% H2/Ar). The key intermediate step of the process is the formation of RE carbodiimides (RE2(CN2)3) along with Pt particles. This synthesis mechanism suggests an efficient strategy to prepare nanoalloys with highly reactive metals.

Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts.

The graphitic-layer encapsulated iron-containing nanoparticles (G@Fe) have been proposed as a potential type of active and stable non-precious metal electrocatalysts (NPMCs) for the oxygen reduction reaction (ORR). However, the contribution of the encapsulated components to the ORR activity is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN-) in alkaline and thiocyanate (SCN-) in acidic media, the metal containing active sites are electrochemically probed. Three representative catalysts are chosen for a comparison including the as-prepared encapsulated G@Fe, commercial Fe/N/C catalyst with iron-nitrogen coordinated surface functionalities and molecular iron phthalocyanine (FePc) containing well-defined structures and compositions. It was found that all samples showed significant shifts of half-wave potentials indicating that surface Fe coordinated sites in all cases. The G@Fe catalyst showed the weakest poisoning effect (the lowest shifts of half-wave potential) compared to the Fe/N/C and FePc catalysts in both electrolytes. These results could be explained that the encapsulated iron components influence the FeNx/C and/or NxC surface functionality.