Engineering phase and surface composition of Pt3Co nanocatalysts: A strategy for enhancing CO tolerance

Improving the CO tolerance of Pt-based catalysts is very meaningful for the application in proton exchange membrane fuel cells and direct alcohol fuel cells. The behavior of Pt-based bimetallic catalysts is depended on their phase and surface composition. In this work, we tuned the surface composition of Pt3Co nanocatalysts by heat treatment under different atmosphere. The results of atomic-resolution HAADF-STEM, XRD, XPS and electrochemical characterization demonstrated that the surface composition of Pt3Co catalysts with Co increased, Intermetallic and Pt-increased were obtained by metal segregation approach. Due to the differences in the surface atomic distribution and alloying extent, the nanocatalysts show different CO poisoning tolerance in the order of Co-increased > Intermetallic > Pt-increased. CO stripping voltammetry and in-situ Fourier transform infrared spectroscopy (FTIRS) were used together to investigate the origin of varied CO poisoning tolerance on three Pt3Co catalysts. The results illustrated that electronic effect plays a major role in weakening CO adsorption on Pt3Co nanocatalysts and thus promoting CO oxidation to form COOHad intermediate consistent with Langmuir-Hinselwood mechanism. Oxophilic effect promotes the oxidation of COOHad intermediate into the final products CO2/CO32-. This work provides a new insight into tuning phase and surface composition of catalysts thus enhancing CO tolerance of Pt-based bimetallic catalysts.