Surface Electronic/Atomic Structure and Activation Energy on Pt(111), Pt3Cu(111), and PtCu(111) for PEFC Cathode

Theoretical analysis of oxygen reduction reaction (ORR) on cathode Pt(111), Pt3Cu(111), and PtCu(111) surfaces in a polymer electrolyte fuel cell (PEFC) is performed to investigate the ORR mechanisms on Pt(111) and the effect of alloying. From density functional theory (DFT) calculations, we found that the difference in adsorption energy of O2 molecules on the surface has a strong relation with the number of d-electrons and the position of the d-band center of the surface Pt atoms. From the results of the activation energy calculations using the unity bond index-quadratic exponential potential (UBI-QEP) method, we show that the oxygen atom coverage on Pt(111) surface has a strong influence on the ORR activity. In addition, it was found that Pt3Cu(111) and PtCu(111) surfaces have lower coverage compared with that of Pt(111) surface, which results in the enhancement of ORR activity.