Support induced charge transfer effects on electrochemical characteristics of Pt nanoparticle electrocatalysts

The electrokinetic properties of Pt nanoparticles supported on Carbon (Pt/C) and Boron Carbide-Graphite composite (Pt/BC) are compared over a wide potential range. The influence of the support on the electronic state of Pt was investigated via in-situ X-ray Absorption Spectroscopy. Pt d-band filling, determined from XANES white line analysis, was lower and nearly constant between 0.4 and 0.95 V vs. RHE for Pt/BC, indicating more positively charged particles in the double layer region and a delay in the onset of oxide formation by about 0.2 V compared to the Pt/C catalyst, which showed a marked increase in d-band vacancies above 0.8 V vs. RHE. Moreover, Δμ analysis of the XANES data indicated a lack of sub-surface oxygen for the Pt/BC catalyst compared to the Pt/C catalyst above 0.9 V vs. RHE. Additional anion adsorption on the Pt/BC in the double layer region, detected by CO displacement, was also confirmed by XANES analysis of the d-band occupancy. The H2 oxidation activities of electrodes with low catalyst loadings were assessed under high mass transport conditions using the floating electrode methodology. The metal-support interaction between the Pt and BC support improved the maximum hydrogen oxidation current density by 1.4 times when compared to Pt/C.