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Spin occupancy regulation of the Pt d-orbital for a robust low-Pt catalyst towards oxygen reduction.

ABSTRACT: Disentangling the limitations of O-O bond activation and OH* site-blocking effects on Pt sites is key to improving the intrinsic activity and stability of low-Pt catalysts for the oxygen reduction reaction (ORR). Herein, we integrate of PtFe alloy nanocrystals on a single-atom Fe-N-C substrate (PtFe@Fe_SAs-N-C) and further construct a ferromagnetic platform to investigate the regulation behavior of the spin occupancy state of the Pt d-orbital in the ORR. PtFe@Fe_SAs-N-C delivers a mass activity of 0.75 A mg_Pt^-1 at 0.9 V and a peak power density of 1240 mW cm^-2 in the fuel-cell, outperforming the commercial Pt/C catalyst, and a mass activity retention of 97%, with no noticeable current drop at 0.6 V for more than 220 h, is attained. Operando spectroelectrochemistry decodes the orbital interaction mechanism between the active center and reaction intermediates. The Pt dz² orbital occupation state is regulated to t_2g⁶e_g³ by spin-charge injection, suppressing the OH* site-blocking effect and effectively inhibiting H₂O₂ production. This work provides valuable insights into designing high-performance and low-Pt catalysts via spintronics-level engineering.

SUBMITTER: Xue D

PROVIDER: S-EPMC11252259 | biostudies-literature | 2024 Jul

REPOSITORIES: biostudies-literature

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Spin occupancy regulation of the Pt d-orbital for a robust low-Pt catalyst towards oxygen reduction.

Xue Dongping D Yuan Yifang Y Yu Yue Y Xu Siran S Wei Yifan Y Zhang Jiaqi J Guo Haizhong H Shao Minhua M Zhang Jia-Nan JN

Nature communications 20240716 1

Disentangling the limitations of O-O bond activation and OH* site-blocking effects on Pt sites is key to improving the intrinsic activity and stability of low-Pt catalysts for the oxygen reduction reaction (ORR). Herein, we integrate of PtFe alloy nanocrystals on a single-atom Fe-N-C substrate (PtFe@Fe<sub>SAs</sub>-N-C) and further construct a ferromagnetic platform to investigate the regulation behavior of the spin occupancy state of the Pt d-orbital in the ORR. PtFe@Fe<sub>SAs</sub>-N-C deliv ...[more]

PMID: 39013873

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Project description:Polymer electrolyte membrane fuel cells (PEMFCs) have reached the commercialization phase, representing a promising approach to curbing carbon emissions. However, greater durability of PEMFCs is of paramount importance to ensure their long-term viability and effectiveness, and catalyst development has become a focal point of research. Pt nanoparticles supported on carbon materials (Pt/C) are the primary catalysts used in PEMFCs. Accomplishing both a high dispersion of uniform metal particles on the carbon support and robust adhesion between the metal particles and the carbon support is imperative for superior stability, and will thereby, advance the practical applications of PEMFCs in sustainable energy solutions. Ultrasound-assisted polyol synthesis (UPS) has emerged as a suitable method for synthesizing catalysts with a well-defined metal-support structure, characterized by the high dispersion and uniformity of metal nanoparticles. In this study, we focused on the effect of ultrasound on the synthesis of Pt/C via UPS and the resulting enhanced stability of Pt/C catalysts. Therefore, we compared Pt/C synthesized using a conventional polyol synthesis (Pt/C_P) and Pt/C synthesized via UPS (Pt/C_U) under similar synthesis conditions. The two catalysts had a similar Pt content and the average particle size of the Pt nanoparticles was similar; however, the uniformity and dispersion of Pt nanoparticles in Pt/C_U were better than those of Pt/C_P. Moreover, ex/in-situ analyses performed in a high-temperature environment, in which nanoparticles tend to agglomerate, have revealed that Pt/C_U exhibited a notable improvement in the adhesion of Pt particles to the carbon support compared with that of Pt/C_P. The enhanced adhesion is crucial for maintaining the stability of the catalyst, ultimately contributing to a better durability in practical applications. Ultrasound was applied to the carbon support without the Pt precursor under the same UPS conditions used to synthesize Pt/C_U to identify the reason for the increased adhesion between the Pt particles and the carbon support in Pt/C_U, and we discovered that oxygen functional groups (C-O, C = O, and O-C = O) for anchoring site of Pt particles were generated in the carbon support. Pt/C_U displayed an increase in stability in an electrochemical accelerated stress test (AST) in an acidic electrolyte. The physical and chemical effects of ultrasound on the synthesis of Pt/C via UPS were identified, and we concluded that UPS is suitable for synthesizing carbon supported electrocatalysts with high stability.

Dataset Information

Spin occupancy regulation of the Pt d-orbital for a robust low-Pt catalyst towards oxygen reduction.

Publications

Spin occupancy regulation of the Pt d-orbital for a robust low-Pt catalyst towards oxygen reduction.

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