Research ArticlePHYSICAL SCIENCE

Efficient oxygen reduction catalysis by subnanometer Pt alloy nanowires

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Science Advances  24 Feb 2017:
Vol. 3, no. 2, e1601705
DOI: 10.1126/sciadv.1601705
  • Fig. 1 Morphology and structure characterizations of subnanometer Pt NWs.

    Representative (A) STEM image, (B) TEM image, (C) TEM-EDS spectrum, (D) PXRD pattern, and (E) HRTEM image of subnanometer Pt NWs. The standard diffraction (Pt, JCPDS no. 04-0802) is drawn using blue lines in (D). The left inset of (A) shows the SAED of subnanometer Pt NWs. The right inset of (A) shows the histograms of diameter and length of subnanometer Pt NWs.

  • Fig. 2 Morphology and structure characterizations of subnanometer PtNi NWs.

    Representative (A and B) STEM and (C) TEM images of subnanometer PtNi NWs. (D) TEM and (E) HRTEM images of two PtNi NWs. (F) TEM-EDS spectrum and (G) PXRD pattern of subnanometer PtNi NWs. The standard diffraction (Pt, JCPDS no. 04-0802) is drawn using blue lines in (G). Left inset of (A) shows SAED pattern of subnanometer PtNi NWs. Right inset of (A) shows the histograms on the diameter and length of subnanometer PtNi NWs.

  • Fig. 3 Morphology and structure characterizations of subnanometer PtCo and PtNiCo NWs.

    Representative STEM (A and C) and HRTEM (B and D) images of subnanometer (A and B) PtCo and (C and D) PtNiCo NWs.

  • Fig. 4 Electrocatalytic performance of PtNiCo NWs/C, PtNi NWs/C, Pt NWs (1 nm)/C, Pt NWs (4.5 nm)/C, and commercial Pt/C.

    (A) CVs recorded at room temperature in 0.1 M HClO4 solution at a sweep rate of 50 mV/s. (B) ORR polarization curves recorded at room temperature in an O2-saturated 0.1 M HClO4 aqueous solution at a sweep rate of 10 mV/s and a rotation rate of 1600 rpm. (C) ECSAs, (D) mass activities, and (E) specific activities of PtNiCo NWs/C, PtNi NWs/C, Pt NWs (1 nm)/C, Pt NWs (4.5 nm)/C, and commercial Pt/C.

  • Fig. 5 Electrocatalytic durability of subnanometer PtNiCo NWs, PtNi NWs, and commercial Pt/C.

    ORR polarization curves of (A) Pt/C, (C) PtNi NWs, and (E) PtNiCo NWs before and after different potential cycles between 0.6 and 1.1 V versus RHE. The ORR polarization curves were recorded at room temperature in an O2-saturated 0.1 M HClO4 aqueous solution at a sweep rate of 10 mV/s and rotation rate of 1600 rpm. The changes in ECSA and mass activities of (B) Pt/C, (D) PtNi NWs, and (F) PtNiCo NWs before and after different potential cycles.

  • Fig. 6 DFT calculations of EO.

    (A) Atomic model of the single crystalline NW with four (111) facets and two (100) facets. (B) Four stable adsorption sites for oxygen on the NW. Red spheres represent oxygen atoms. (C) ΔEO on flat Pt (111) surface and Pt-based NWs. The black squares and red circles correspond to ΔEO values on the pure Pt and PtNi NW, respectively. The horizontal dashed line indicates the optimal ΔEO value.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/2/e1601705/DC1

    fig. S1. TEM, HAADF-STEM images, and histograms of diameter and length of Pt NWs.

    fig. S2. XPS spectra of Pt NWs.

    fig. S3. Additional HRTEM images of Pt NWs.

    fig. S4. TEM, HAADF-STEM images, and histograms of diameter and length of PtNi NWs.

    fig. S5. Additional TEM and HRTEM images of PtNi NWs.

    fig. S6. STEM image and EDS line scan of PtNi NWs.

    fig. S7. TEM images, histograms of diameter and length, PXRD pattern, and EDS pattern of PtCo NWs.

    fig. S8. TEM images, histograms of diameter and length, PXRD pattern, and EDS pattern of PtNiCo NWs.

    fig. S9. STEM image and EDS line scan of PtNiCo NWs.

    fig. S10. TEM images, histograms of diameter and length, PXRD pattern, and EDS pattern of 9-nm Pt NWs and 35-nm Pt NWs.

    fig. S11. TEM images of diameter and length changes of Pt NW intermediates obtained with different reaction times.

    fig. S12. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but changing Mo(CO)6.

    fig. S13. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but changing Ni(acac)2.

    fig. S14. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but changing Ni(acac)2 with Fe(acac)2.

    fig. S15. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but with different amount of CTAC.

    fig. S16. Fourier transform infrared spectroscopy spectrum of PtNi NWs/C.

    fig. S17. TEM images of Pt NWs on commercial carbon.

    fig. S18. TEM images of PtNi NWs on commercial carbon.

    fig. S19. TEM images of PtNiCo NWs on commercial carbon.

    fig. S20. TEM image and diameter histogram of Pt NWs with the diameter of 4.5 nm.

    fig. S21. ORR polarization curves, CVs, mass, and specific activities of Pt NWs with different lengths.

    fig. S22. TEM images of commercial Pt/C.

    fig. S23. CVs of Pt/C, PtNi NWs/C, and PtNiCo NWs/C before and after 30,000 cycles.

    fig. S24. TEM image, EDS pattern, and EDS line scan of PtNi NWs/C after 30,000 cycles.

    fig. S25. TEM image, EDS pattern, and EDS line scan of PtNiCo NWs/C after 30,000 cycles.

    fig. S26. TEM images of commercial Pt/C catalyst after 30,000 cycles.

    fig. S27. TEM, PXRD pattern, and EDS pattern of Pt84.4Ni15.6 NWs.

    fig. S28. TEM, PXRD pattern, and EDS pattern of Pt64.6Ni35.4 NWs.

    fig. S29. TEM, PXRD pattern, and EDS pattern of Pt78.5Co21.5 NWs.

    fig. S30. TEM, PXRD pattern, and EDS pattern of Pt67.1Ni23.0Co9.9 NWs.

    fig. S31. Image of ~50-ml PtNi NW colloidal solution and TEM images of PtNi NWs.

    table S1. Atomic ratios of PtNi NWs and PtNiCo NWs characterized by ICP, EDS, and XPS.

    table S2. Performance comparisons of various Pt-based NWs and this work.

    References (5055)

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. TEM, HAADF-STEM images, and histograms of diameter and length of Pt NWs.
    • fig. S2. XPS spectra of Pt NWs.
    • fig. S3. Additional HRTEM images of Pt NWs.
    • fig. S4. TEM, HAADF-STEM images, and histograms of diameter and length of PtNi NWs.
    • fig. S5. Additional TEM and HRTEM images of PtNi NWs.
    • fig. S6. STEM image and EDS line scan of PtNi NWs.
    • fig. S7. TEM images, histograms of diameter and length, PXRD pattern, and EDS pattern of PtCo NWs.
    • fig. S8. TEM images, histograms of diameter and length, PXRD pattern, and EDS pattern of PtNiCo NWs.
    • fig. S9. STEM image and EDS line scan of PtNiCo NWs.
    • fig. S10. TEM images, histograms of diameter and length, PXRD pattern, and EDS pattern of 9-nm Pt NWs and 35-nm Pt NWs.
    • fig. S11. TEM images of diameter and length changes of Pt NW intermediates obtained with different reaction times.
    • fig. S12. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but changing Mo(CO)6.
    • fig. S13. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but changing Ni(acac)2.
    • fig. S14. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but changing Ni(acac)2 with Fe(acac)2.
    • fig. S15. TEM images of the products collected from the reaction with the same condition used in the synthesis of unique Pt NWs but with different amount of CTAC.
    • fig. S16. Fourier transform infrared spectroscopy spectrum of PtNi NWs/C.
    • fig. S17. TEM images of Pt NWs on commercial carbon.
    • fig. S18. TEM images of PtNi NWs on commercial carbon.
    • fig. S19. TEM images of PtNiCo NWs on commercial carbon.
    • fig. S20. TEM image and diameter histogram of Pt NWs with the diameter of 4.5 nm.
    • fig. S21. ORR polarization curves, CVs, mass, and specific activities of Pt NWs with different lengths.
    • fig. S22. TEM images of commercial Pt/C.
    • fig. S23. CVs of Pt/C, PtNi NWs/C, and PtNiCo NWs/C before and after 30,000 cycles.
    • fig. S24. TEM image, EDS pattern, and EDS line scan of PtNi NWs/C after 30,000 cycles.
    • fig. S25. TEM image, EDS pattern, and EDS line scan of PtNiCo NWs/C after 30,000 cycles.
    • fig. S26. TEM images of commercial Pt/C catalyst after 30,000 cycles.
    • fig. S27. TEM, PXRD pattern, and EDS pattern of Pt84.4Ni15.6 NWs.
    • fig. S28. TEM, PXRD pattern, and EDS pattern of Pt64.6Ni35.4 NWs.
    • fig. S29. TEM, PXRD pattern, and EDS pattern of Pt78.5Co21.5 NWs.
    • fig. S30. TEM, PXRD pattern, and EDS pattern of Pt67.1Ni23.0Co9.9 NWs.
    • fig. S31. Image of ~50-ml PtNi NW colloidal solution and TEM images of PtNi NWs.
    • table S1. Atomic ratios of PtNi NWs and PtNiCo NWs characterized by ICP, EDS, and XPS.
    • table S2. Performance comparisons of various Pt-based NWs and this work.
    • References (50–55)

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