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Carbon nanotubes with the defects from the graphite-like phosphorus exhibit high activity for the hydrogen evolution reaction

AI Jie LIU Zi-wu SUN Mao-mao LIU Ling WANG Quan-de

艾杰, 刘滋武, 孙毛毛, 刘玲, 王全德. 石墨磷引起的缺陷碳纳米管展现出较高的氢析出活性[J]. 新型炭材料. doi: 10.1016/S1872-5805(21)60023-10
引用本文: 艾杰, 刘滋武, 孙毛毛, 刘玲, 王全德. 石墨磷引起的缺陷碳纳米管展现出较高的氢析出活性[J]. 新型炭材料. doi: 10.1016/S1872-5805(21)60023-10
AI Jie, LIU Zi-wu, SUN Mao-mao, LIU Ling, WANG Quan-de. Carbon nanotubes with the defects from the graphite-like phosphorus exhibit high activity for the hydrogen evolution reaction[J]. NEW CARBOM MATERIALS. doi: 10.1016/S1872-5805(21)60023-10
Citation: AI Jie, LIU Zi-wu, SUN Mao-mao, LIU Ling, WANG Quan-de. Carbon nanotubes with the defects from the graphite-like phosphorus exhibit high activity for the hydrogen evolution reaction[J]. NEW CARBOM MATERIALS. doi: 10.1016/S1872-5805(21)60023-10

石墨磷引起的缺陷碳纳米管展现出较高的氢析出活性

doi: 10.1016/S1872-5805(21)60023-10

Carbon nanotubes with the defects from the graphite-like phosphorus exhibit high activity for the hydrogen evolution reaction

More Information
  • 摘要: 作为一种新型碳基析氢反应催化剂,磷掺杂碳材料近年来已引起了人们极大关注。然而到目前为止,磷掺杂碳材料中的C-P物种对于氢析出活性的作用尚未被揭示。为了探讨碳基催化剂中C-P物种对其氢析出性能的影响,我们制备了四种具有不同石墨、吡啶、吡咯类磷物种分布的磷掺杂碳纳米管,并探讨了这三种磷物种的含量和氢析出活性之间的关系。结果表明在酸性介质中,一种在电流密度为10 mA cm−2 时过电位为0.266 V的磷掺杂碳纳米管展现出较高的氢析出活性。同时,密度泛函理论计算表明较高的氢析出性能主要是由石墨磷分解产生的五元环和九元环缺陷所引起,这为磷掺杂碳基催化剂表面的析氢反应提供一更为深入的理解。
  • Figure  1.  The SEM images of PDCNTs1 (a), PDCNTs2 (d), PDCNTs3 (g) and PDCNTs4 (j). The TEM images of PDCNTs1 (b, c), PDCNTs2 (e, f), PDCNTs3 (h, i) and PDCNTs4 (k, l), and their HRTEM images inserted their corresponding TEM image (c, f, i and l).

    Figure  2.  Deconvoluted Raman spectra and ID/IG values of PDCNTs1 (a), PDCNTs2 (b), PDCNTs3 (c) and PDCNTs4 (d).

    Figure  3.  The high-resolution C1s spectra of PDCNTs1 (a), PDCNTs2 (b), PDCNTs3 (c) and PDCNTs4 (d).

    Figure  4.  The high-resolution P2p spectra of PDCNTs1 (a), PDCNTs2 (b), PDCNTs3 (c) and PDCNTs4 (d).

    Figure  5.  The HER polarization curves of PDCNTs1, PDCNTs2, PDCNTs3, PDCNTs4 and 40 wt% Pt/C catalysts in N2-saturated 0.5 M H2SO4 solution (a). Their corresponding overpotentials at the current density of 10 mA cm−2 (b) and tafel plots (c) from (a). The dependences of HER current densities (at 300 mV overpotential) of PDCNTs1 (■), PDCNTs2 (■), PDCNTs3 (■), PDCNTs4 (■) on the C-P contents and the values of ID/IG (d). Impedence diagrams of PDCNTs1, PDCNTs2, PDCNTs3, and PDCNTs4 (e). The HER curves of PDCNTs4 in 0.5 M H2SO4 medium before and after 1000 cycles (f).

    Figure  6.  Cyclic voltammograms of PDCNTs1, PDCNTs2, PDCNTs3 and PDCNTLs4 in 0.5 M H2SO4 at different scan rates, respectively (a-d).

    Figure  7.  The capacitive currents as a function of scan rate for PDCNTs1, PDCNTs2, PDCNTs3 and PDCNTs4.

    Figure  8.  The CNTs with a C3-P graphite-like configuration (a) the blank normal CNT framework (b) and the CNTs with the pentagon- and nine-membered ring defects (c) after the decomposition of C3-P group.

    Figure  9.  The possible forming ways of pentagon- and nine-membered ring defects with the decomposition of the C3-P group.

    Figure  10.  The possible HER routes on PDCNTs in acidic medium.

    Table  1.   Elemental contents (at. %) in four samples from the XPS analyses.

    SamplesCOP
    C—PC3-P=OC—O—PC—P—O
    PDCNTs193.126.520.1910.1090.0320.028
    PDCNTs297.522.200.1310.0820.0670
    PDCNTs397.981.790.1190.0390.0720
    PDCNTs498.271.730000
    下载: 导出CSV

    Table  2.   The contents of sp2 and sp3 carbon, C=O, C—O, π-π* and the ratios of sp2/sp3 carbon from the C1s spectra.

    Samplessp2sp3sp3/sp2C-Oπ-π*
    PDCNTs169.748.7712.5810.8010.69
    PDCNTs266.8210.8416.226.1413.73
    PDCNTs366.7611.6617.466.5812.98
    PDCNTs466.0714.4021.795.0812.71
    下载: 导出CSV

    Table  3.   The charge and spin densities of carbon atoms in the new formed defects after the decomposition of C3-P graphite-like structure and those of the corresponding carbon atoms in the blank.

    Carbon atomCharge density (blank)Spin density (blank)Charge density(after pyrolysis)Spin density
    (after pyrolysis)
    1−0.0090−0.0260
    2000.0380
    300−0.0670
    40.0180−0.0090
    5−0.0140−0.0630
    6−0.01400.0340
    70.03500.0300
    8−0.1530−0.1430
    90.0160−0.0420
    100.0020−0.0730
    110.0020−0.0460
    12−0.02100.0090
    130.0190
    下载: 导出CSV

    Table  4.   The adsorption energies of carbon atoms with large altered negative charges in the new formed defects from the decomposition of C3-P graphite-like structure and those of corresponding carbon atoms in the blank.

    adsorption energies
    (kcal mol−1)
    Carbon atom
    Pure CNT (blank)CNT (after pyrolysis)
    1−58.163−74.825
    3−56.805−101.009
    4−55.909−113.664
    5−58.719−101.588
    9−55.458−80.907
    10−55.824−142.826
    11−57.595−75.465
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-01-01
  • 修回日期:  2021-01-01
  • 网络出版日期:  2021-03-16

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