The strong Pt-N3O coordination in graphene nanosheets accelerates the 4e− electrocatalytic oxygen reduction process

doi:10.1016/S1872-2067(25)64768-1

Abstract

Abstract:

Single-metal sites anchored in nitrogen-doped nanocarbons are recognized as potent electrocatalysts for applications in energy conversion and storage. Here, an innovative inorganic salt-mediated secondary calcination strategy was developed to construct robust Pt single-atom catalysts on nitrogen- and oxygen-doped graphene nanosheets (Pt-N/O-GNs), thereby significantly enhancing the efficiency of the electrocatalytic oxygen reduction reaction (ORR). The ultrathin N/O-GNs, obtained by stripping Zn-ZIF with auxiliaries of KCl and LiCl, provide stable anchoring sites for highly exposed Pt-N₃O active structures. The Pt-N/O-GNs catalyst, featuring a low Pt loading of 0.44 wt%, demonstrates exceptional mass activity in the ORR process. It attains an impressive onset potential of 0.99 V and a half-wave potential of 0.88 V. The zinc-air battery driven by the Pt-N/O-GNs displays superior power density and cycle stability. Theoretical computational studies reveal that the structure of heteroatoms doped in few-layer graphene facilitates the stable anchoring of single-atom configurations. The findings provide new perspectives for the tailored design and fabrication of single-metal-site electrocatalysts.

Key words: Oxygen reduction reaction, Pt-N₃O active center, Pt single atom, Ultra-thin carbon layer, Metal-support interaction

Xinqi Wang, Xueyuan Zhang, Menggai Jiao, Runlin Ma, Fang Xie, Hao Wan, Xiangjian Shen, Li-Li Zhang, Wei Ma, Zhen Zhou. The strong Pt-N₃O coordination in graphene nanosheets accelerates the 4e⁻ electrocatalytic oxygen reduction process[J]. Chinese Journal of Catalysis, 2025, 77: 227-235.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64768-1

https://www.cjcatal.com/EN/Y2025/V77/I10/227

Figures/Tables 5

Fig. 1. (a) Schematic representation of the synthesis processes for Pt-N/O-GNs derived from Zn-ZIF. HR-TEM images (b), AC-STEM image (c), and HAADF-STEM image and EDS elements mapping (d) of Pt, C, N in Pt-N/O-GNs.

Fig. 2. XPS curves of N 1s (a), O 1s (b), and Pt 4f (c) orbitals for prepared Pt-based samples. Pt L3-edge XANES spectra (d) and The k2-weighted FT-EXAFS spectra (e) of Pt-N/O-GNs, Pt, and PtO2, respectively. (f) Corresponding XAFS spectrum fitting curve in k2 space for Pt in Pt-N/O-GNs. WT of Pt in Pt foil (g), PtO2 (h), and Pt-N/O-GNs (i).

Fig. 3. Electrocatalytic ORR performance tests of catalysts. (a) LSV curves. (b) ORR activities comparison. (c) Tafel slopes. (d) Cdl values. (e) LSV curves obtained at various rotating rates in 0.1 mol L-1 KOH, and the fitted K-L plots and the calculated electron transfer number (n) in the inserted graph. (f) n value and HO2?% for Pt-N/O-GNs evaluated by RRDE methods.

Fig. 4. Electrocatalytic stability and Zn-air battery performance tests. (a) LSV curves of Pt-N/O-GNs at 1600 rpm at 5 mV s?1 before and after 5000 CV cycles for ORR in 0.1 mol L?1 KOH. (b) Chronopotentiometry measurements on Pt/C and Pt-N/O-GNs electrodes. (c) LSV curves of Pt-N/O-GNs and Pt/C in O2-saturated 0.1 mol L?1 KOH and mixed electrolyte by adding 0.5 mol L?1 CH3OH. (d) CV curves of Pt/C and Pt-N/O-GNs in N2-saturated 0.1 mol L?1 KOH + 0.5 mol L?1 CH3OH (i), and chronoamperometric response of Pt-N/O-GNs at 0.75 V under 1600 rpm after adding methanol at 200 s in O2-saturated 0.1 mol L?1 KOH (ii). (e) Charge/discharge polarization and power density curves of the ZAB based on Pt-N/O-GNs and Pt/C catalysts, respectively. (f) Galvanostatic discharge-charge cycle curves of the ZAB with Pt-N/O-GNs electrode at 10 mA cm?2.

Fig. 5. Mechanism analysis of catalysts. Schematic diagram (a) and free energy comparison (b) of the possible 2e? or 4e? ORR pathway on the Pt-N3O center in monolayer carbon. (c) The configurations of different adsorption products of Pt binding on monolayer carbon substrates.

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The strong Pt-N₃O coordination in graphene nanosheets accelerates the 4e⁻ electrocatalytic oxygen reduction process

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