Density functional theory study of active sites and reaction mechanism of ORR on Pt surfaces under anhydrous conditions

doi:10.1016/S1872-2067(22)64125-1

Abstract

Abstract:

Identifying active sites and catalytic mechanism of the oxygen reduction reaction under anhydrous conditions are crucial for the development of next generation proton exchange membrane fuel cells (PEMFCs) operated at a temperature > 100 °C. Here, by employing density functional theory calculations, we studied ORR on flat and stepped Pt(111) surfaces with both (110) and (100) type of steps. We found that, in contrast to ORR under hydrous conditions, (111) terrace sites are not active for ORR under anhydrous conditions, because of weakened binding of ORR intermediates induced by O* accumulation on the surface. On the other hand, step edges, which are generally not active for ORR under hydrous conditions, are predicted to be the active sites for ORR under anhydrous conditions. Among them, (110) type step edge with a unique configuration of accumulated O stabilizes O₂ adsorption and facilitates O₂ dissociation, which lead an overpotential < 0.4 V. To improve ORR catalysts in high-temperature PEMFCs, it is desirable to maximize (110) step edge sites that present between two (111) facets of nanoparticles.

Key words: Oxygen reduction, Active site, Anhydrous condition, High-temperature PEMFCs, Density functional theory

Guangdong Liu, Huiqiu Deng, Jeffrey Greeley, Zhenhua Zeng. Density functional theory study of active sites and reaction mechanism of ORR on Pt surfaces under anhydrous conditions[J]. Chinese Journal of Catalysis, 2022, 43(12): 3126-3133.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64125-1

https://www.cjcatal.com/EN/Y2022/V43/I12/3126

Figures/Tables 6

Fig. 1. Reaction free energy of the associative mechanism and the surface phase diagram on Pt(111) surface. Free energy diagram of ORR without (a) and with (c) O* accumulation on Pt(111) under anhydrous conditions. As a comparison, the reaction free energy on clean Pt(111) under hydrous condition is also given. The red and blue solid lines represent reaction free energy at the potential that all reaction steps are down-hill and at the equilibrium potential (U = 1.23 V), respectively. (b) Surface phase diagram for O adsorption on Pt(111) surface at 126.85 °C.

Fig. 2. Reaction free energy diagram of ORR on Pt(111) with dissociative mechanism under anhydrous conditions. Reaction free energy without (a) and with (b) O* accumulation on the surface.

Fig. 3. Reaction free energy diagram of ORR with associative mechanism and surface phase diagram on stepped Pt(111) surface under anhydrous conditions. Reaction free energy on clean Pt(332) and Pt(322) (a). Surface phase diagram for O adsorption on Pt(332) (b) and Pt(322) (c).

Fig. 4. Reaction free energy diagram of ORR with associative mechanism on O* accumulated stepped Pt(111) surface. Reaction free energy on Pt(332) with 0.2 ML O* accumulation (a) and Pt(322) with 0.4 ML O* accumulation (b).

Fig. 5. Dissociative mechanism on Pt(332) with 0.2 ML O* accumulation (a), Pt(322) with 0.3 ML O accumulation (b) and Pt(322) with 0.4 ML O* accumulation (c) under anhydrous conditions.

Fig. 6. Transition states and dissociation barrier for O2 dissociation on flat and stepped Pt(111) surfaces. Transition states on Pt(111) (a), Pt(332) (c) and Pt(322) (e) without O* accumulation, and Pt(111) with 0.25 ML O* accumulation (b), Pt(332) with 0.2 ML O* accumulation (d) and Pt(322) with 0.4 ML O* accumulation (f). Ea is O2 dissociation barrier. An orange dashed outline indicates a Pt(111)-(2 × 2)-fcc-O structure.

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