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Study of Mechanisms of CO and NO2 Oxidation on Zn–CNT (6, 0) and Zn–BNNT (6, 0), Mn–B38N38 and Mn–C76

Zhi-Wen ZENG ,  Xiang LI ,  Fu-Xing ZHANG ,  Meysam NAJAFI

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Citation:  Zhi-Wen ZENG, Xiang LI, Fu-Xing ZHANG, Meysam NAJAFI. Study of Mechanisms of CO and NO2 Oxidation on Zn–CNT (6, 0) and Zn–BNNT (6, 0), Mn–B38N38 and Mn–C76[J]. Chinese Journal of Structural Chemistry, 2020, 39(1): 41-47. doi: 10.14102/j.cnki.0254-5861.2011-2461 shu

Study of Mechanisms of CO and NO2 Oxidation on Zn–CNT (6, 0) and Zn–BNNT (6, 0), Mn–B38N38 and Mn–C76

English

  • 1. INTRODUCTION

    The metal-based catalysts have been used to oxidize the toxic molecules with high cost and low abilities at normal temperature. Recently, carbon nano catalysts with high efficiency and low price have been used as novel catalysts to oxidize the toxic molecules[1-6]. The carbon nanotubes and nanocages are active catalysts to oxidize the nitrogen dioxide (NO2) carbon monoxide (CO) at normal temperature[7-12]. The metal doped carbon nanotubes and nanocages have higher catalytic activity than metal-based catalysts, significantly[13-18]. The nanotubes and nanocages as catalysts can oxidize the toxic molecules through the Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms[19-21].

    Here, the oxidation of nitrogen dioxide (NO2) on the surfaces of Mn-doped carbon nanocage (Mn–C76) and Mn-doped boron nitride nanocage (Mn–B38N38) and that of carbon monoxide (CO) on the surfaces of Zn-doped carbon nanotube (Zn–CNT (6, 0)) and Zn-doped boron nitride nanotube (Zn–BNNT (6, 0)) are investigated. The important goals of this study are to (a) find acceptable mechanisms to the oxidation of NO2 and CO; (b) compare the performances of Mn–C76 and Mn–B38N38 to NO2 oxidation; (c) compare the abilities of Zn–CNT (6, 0) and Zn–BNNT (6, 0) to CO oxidation; and (d) propose the optimum reaction paths to NO2 and CO oxidation.

    2. COMPUTATIONAL DETAILS

    The geometries of nanocages (Mn–B38N38 and Mn–C76), nanotubes (Zn–CNT (6, 0) and Zn–BNNT (6, 0)) and their complexes with molecules are optimised in GAMESS by DFT/M06-2X/6311G+(2d, 2p) method[22-28]. The ∆Ead values of molecules on nanocages (Mn–B38N38 and Mn–C76), nanotubes (Zn–CNT (6, 0) and Zn–BNNT (6, 0)) are ∆Ead = Ecomplex – Enano – Emolecule. The ∆G values of oxidation reactions of NO2 and CO on nanocages (Mn–B38N38 and Mn–C76), nanotubes (Zn–CNT (6, 0) and Zn–BNNT (6, 0)) are ∆G = ∆H – T∆S[29-40].

    3. RESULTS AND DISCUSSION

    Structures of Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are reported in Fig. 1. Adsorption energies (∆Ead) Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –2.22, –2.38, –2.15 and –2.26 eV, respectively. In Fig. 1, NO2 is joined to Mn–C76 and Mn–B38N38 through O atom with ∆Ead to be –0.84 and –0.95 eV. In Fig. 1, CO is joined to Zn–CNT (6, 0) and Zn–BNNT (6, 0) through O atom and ∆Ead values are –0.77 and –0.83 eV. In Fig. 1, O2 is adsorbed on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) through the π and σ orbitals of Mn and Zn, significantly.

    Figure 1

    Figure 1.  Structures and ∆Ead values (eV) of molecules with nanocages and nanotubes
    DownLoad: Full-Size Img PowerPoint

    The ∆Ead values of the most complexes of O2 with Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –0.96, –1.02, –0.89 and –0.98 eV, respectively (in Table 1). In Fig. 1, NO3 is adsorbed on Mn–C76 and Mn–B38N38 through N and O positions and ∆Ead values of the most complexes of NO3 with Mn–C76 and Mn–B38N38 are –1.44 and –1.57 eV, respectively. In Fig. 1, CO is adsorbed on Zn–CNT (6, 0) and Zn–BNNT (6, 0) through C and O positions and ∆Ead values of the most complexes of CO with Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –1.37 and –1.45 eV, respectively.

    Table 1

    Table 1.  Calculated Parameters of Studied Nano Structures
    DownLoad: CSV
    Mn–C76 Mn–B38N38 Zn–CNT (6, 0) Zn–BNNT (6, 0)
    Str. E (eV) E (eV) E (eV) E (eV)
    1 0.00 0.00 0.00 0.00
    2 –0.94 –0.99 –0.92 –0.97
    3 –2.19 –2.27 –2.26 –2.34
    4 –2.03 –2.15 –2.13 –2.25
    5, 6, 12 –2.68 –2.73 –2.68 –2.73
    7 –3.65 –3.78 –3.71 –3.84
    8 –2.28 –2.39 –2.28 –2.39
    9 –2.13 –2.19 –2.17 –2.23
    10 –1.68 –1.81 –1.73 –1.86
    11 –2.28 –2.36 –2.28 –2.36

    Reaction pathways of NO2 and CO oxidation through the ER and LH mechanism on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are described in Fig. 2. The relative energies of intermediates of NO2 and CO oxidation on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are reported in Fig. 2. The structures of intermediates of NO2 and CO oxidation on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are displayed in Fig. 3. In the LH mechanism, O2 is adsorbed on Mn atoms of Mn–C76 and Mn–B38N38 and Zn atoms of Zn–CNT (6, 0) and Zn–BNNT (6, 0). The NO2 and CO molecules are co-adsorbed on Mn-nanocage-O2* and Zn-nanotube-O2*, respectively.

    Figure 2

    Figure 2.  Oxidation of CO and NO2 through LH (violet) and ER (green) mechanisms and relative energies
    DownLoad: Full-Size Img PowerPoint

    Figure 3

    Figure 3.  Intermediates of oxidation of CO and NO2
    DownLoad: Full-Size Img PowerPoint

    The Mn-nanocage-NO2*OO* and Zn-nanotube-CO*OO* complexes are created and Er values on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –1.19, –1.20, –1.25 and –1.26 eV, respectively. Then O–O bonds of Mn-nanocage-NO2*OO* and Zn-nanotube–CO*OO* complexes are braked and Mn-nanocage-O* and Zn-nanotube-O* are created and NO3 and CO2 are released. The Er values on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –0.15, –0.17, –0.11 and –0.13 eV, respectively. The Ea values on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are 0.45, 0.38, 0.44 and 0.37 eV, respectively.

    In the ER mechanism, NO2 and CO molecules are connected to Mn-nanocage-O2* and Zn-nanotube-O2*, respectively and Mn-nanocage-NO2*OO* and Zn-nanotube-CO*OO* complexes are created. The Er values on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –1.25, –1.28, –1.34 and –1.37 eV, respectively. Then O–O bonds of Mn–nanocage–NO2*OO* and Zn-nanotube-CO*OO* complexes are braked. The Ea values of realising NO3 and CO2 on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are 0.16, 0.12, 0.09 and 0.11 eV, respectively.

    The Er values of realising NO3 and CO2 on Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are –0.49, –0.46, –1.03 and –1.11 eV, respectively. In the LH mechanism, the NO2 and CO cannot adsorb the O* of Mn-nanocage-O* and Zn-nanotube-O*, while in ER mechanism they are adsorbed to O* of Mn-nanocage-O* and Zn-nanotube-O* and the second NO3 and CO2 are released, remarkably. Finally, the Mn–C76, Mn–B38N38, Zn– CNT (6, 0) and Zn–BNNT (6, 0) are proposed to oxidize NO2 and CO molecules with high performances at room temperature.

    4. CONCLUSION

    The NO2 and CO oxidation on Mn–C76, Mn– B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are examined, respectively. The Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) can ooxidize the NO2 and CO molecules through the LH and ER mechanisms. The Mn and Zn atoms are catalytic active positions of Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0). The Mn-nanocage-NO2*OO* and Zn-nanotube-CO*OO* complexes in the ER pathway are more stable than LH pathway. In ER and LH pathways, the first and second NO3 and CO2 molecules are released, respectively. Finally, the Mn–C76, Mn–B38N38, Zn–CNT (6, 0) and Zn–BNNT (6, 0) are proposed to the oxidation of NO2 and CO molecules with high performance at room temperature.


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  • Figure 1  Structures and ∆Ead values (eV) of molecules with nanocages and nanotubes

    下载: 全尺寸图片 幻灯片

    Figure 2  Oxidation of CO and NO2 through LH (violet) and ER (green) mechanisms and relative energies

    下载: 全尺寸图片 幻灯片

    Figure 3  Intermediates of oxidation of CO and NO2

    下载: 全尺寸图片 幻灯片

    Table 1.  Calculated Parameters of Studied Nano Structures

    Mn–C76 Mn–B38N38 Zn–CNT (6, 0) Zn–BNNT (6, 0)
    Str. E (eV) E (eV) E (eV) E (eV)
    1 0.00 0.00 0.00 0.00
    2 –0.94 –0.99 –0.92 –0.97
    3 –2.19 –2.27 –2.26 –2.34
    4 –2.03 –2.15 –2.13 –2.25
    5, 6, 12 –2.68 –2.73 –2.68 –2.73
    7 –3.65 –3.78 –3.71 –3.84
    8 –2.28 –2.39 –2.28 –2.39
    9 –2.13 –2.19 –2.17 –2.23
    10 –1.68 –1.81 –1.73 –1.86
    11 –2.28 –2.36 –2.28 –2.36
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  • 发布日期:  2020-01-01
  • 收稿日期:  2019-05-17
  • 接受日期:  2019-11-20
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