Elucidation of the mechanism of melamine adsorption on Pt(111) surface via density functional theory calculations

The oxygen reduction reaction (ORR) activity of Pt catalysts in polymer electrolyte fuel cells (PEFCs) should be enhanced to reduce Pt usage. The adsorption of heteroaromatic ring compounds such as melamine on the Pt surface can enhance its catalytic activity. However, melamine adsorption on Pt and the consequent ORR enhancement mechanism remain unclear. In this study, we performed density functional theory calculations to determine the adsorption structures of melamine/Pt(111). Melamine was coordinated to Pt via two N lone pairs on NH2 and N- in the triazine ring, resulting in a chemisorption structure with slight electron transfer. Four types of adsorption structures were identified: three-point adsorption (two amino groups and a triazine ring: Type A), two-point adsorption (one amino group and a triazine ring: Type B), two-point adsorption (two amino groups: Type C), and one-point adsorption (one amino group: Type D). The most stable structure was Type B. However, multiple intermediate structures were formed owing to the conformational changes from the most stable to other stable adsorption structures. The resonance structures of the adsorbed melamine stabilise the adsorption, as increased resonance allows for more electron delocalisation. In addition, the lone-pair orbital of the amino group in the adsorbed melamine acquires the characteristics of an sp3 hybrid orbital, which prevents horizontal adsorption on the Pt surface. We believe that understanding these adsorption mechanisms will help in the molecular design of organic molecule-decorated Pt catalysts and will lead to the reduction of Pt usage in PEFCs.