First-Principles Study on Pt-Based Sub-Nanocluster Carbon-Metal Hybrid Catalysts for the Oxygen Reduction Reaction
Authors: Lee EO Yoon , Ham Hyung Chul 
Published: November 2022

Recently, the polymer electrolyte membrane fuel cell (PEMFC) has been drawing huge attention as an eco-friendly energy conversion device which can replace an internal combustion engine without environmental contaminant such as CO2 and NOx. However, the use of expensive noble metal catalysts such as Pt is essential for the cathode because the oxygen reduction reaction (ORR) at cathode are kinetically much slower than the hydrogen oxidation at anode. For this reason, many of researchers have vigorously worked on the development of Pt-based alloy catalysts such as Pt-Co and Pt-Ni alloys to reduce noble metal usage, but there are still limitations in catalytic activity and durability for the commercialization.
Herein, to overcome the limitations, we developed Pt-based carbon-metal hybrid catalyst showing high performance for ORR using density functional theory (DFT) calculation. The slab model of Pt-based carbon-metal hybrid catalyst was constructed by Pt sub-nanocluster supported on graphite with graphene-shaped carbon shell on top of the Pt sub-nanocluster. The most stable geometry of the hybrid catalyst was determined by the formation energy, and the ORR mechanism on surface of hybrid catalyst as well as electrochemical activity was investigated. As a result of investigation, we confirmed that the oxygen reduction occurs on active graphene-shaped carbon shell sites. On pure Pt sub-nanocluster hybrid catalyst, once the hydrogen superoxide (OOH) is adsorbed on carbon shell surface after the oxygen adsorption and protonation, the hydrogen peroxide (H2O2) is preferentially formed at higher onset potential than that of four-electron O2 reduction, which the final product is water (H2O). However, the formation of hydrogen peroxide in PEMFC should be avoided owing to creation of radical, resultant degradation of membrane and low energy conversion efficiency. Surprisingly, we identified that the hydrogen peroxide formed on pure Pt sub-nanocluster hybrid catalyst can be decomposed into OH and H2O with low energy barrier, whose value is much lower than desorption energy of produced hydrogen peroxide, so that subsequent reduction reaction can occur. When this four-electron ORR via hydrogen peroxide decomposition takes place, the ORR activity is improved compared to Pt(111) catalyst, where the onset potential of pure Pt sub-nanocluster hybrid catalyst presents is higher than that of Pt(111). Moreover, we introduced Pt-based alloy sub-nanocluster to reduce Pt usage further. The Pt-based alloy sub-nanocluster hybrid catalyst also exhibited increased ORR activity. For Pt-based alloy sub-nanocluster hybrid catalyst, we carried out analysis of density of state and figured out that the more orbital overlap between carbon shell and sub-nanocluster is generated, the higher catalytic activity is shown due to enrichment of electrons on carbon shell surface.
We expect this work can help understanding the mechanism of activity improvement of carbon metal hybrid catalyst, suggesting promising way to design high-performance ORR catalyst with low Pt loadings.