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Pd-Cu催化剂上吸附O强化甲烷活化机理研究

张佳栋 牛俊天 刘海玉 樊保国 金燕

张佳栋, 牛俊天, 刘海玉, 樊保国, 金燕. Pd-Cu催化剂上吸附O强化甲烷活化机理研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022091
引用本文: 张佳栋, 牛俊天, 刘海玉, 樊保国, 金燕. Pd-Cu催化剂上吸附O强化甲烷活化机理研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022091
ZHANG Jia-dong, NIU Jun-tian, LIU Hai-yu, FAN Bao-guo, JIN Yan. Study on the activation mechanism of O-enhanced methane adsorbed on Pd-Cu catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022091
Citation: ZHANG Jia-dong, NIU Jun-tian, LIU Hai-yu, FAN Bao-guo, JIN Yan. Study on the activation mechanism of O-enhanced methane adsorbed on Pd-Cu catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022091

Pd-Cu催化剂上吸附O强化甲烷活化机理研究

doi: 10.19906/j.cnki.JFCT.2022091
基金项目: 国家自然科学基金青年项目(52106179)资助
详细信息
    通讯作者:

    金燕 工学博士 教授 博士生导师,邮箱:jinyan@tyut.edu.cn

  • 中图分类号: TQ426,X701

Study on the activation mechanism of O-enhanced methane adsorbed on Pd-Cu catalyst

Funds: The project was supported by the National Natural Science Foundation of China (No.52106179)
  • 摘要: 甲烷催化燃烧相比较传统燃烧有燃烧温度低,清洁以及高效的优点,在天然气汽车、固体氧化物燃料电池等多个领域具有较好的应用前景。为了揭示甲烷在不同掺杂比的Pd-Cu团簇上脱氢机理,采用密度泛函理论(DFT)对CH4*在不同团簇的直接脱氢和O辅助脱氢上进行计算。计算结果表明:Pd原子的掺杂提高了Cu(111)表面的吸附能力,在直接脱氢过程中,Pd的掺杂不仅使能垒由2.56 eV降低到2.43 eV,而且使速率控制步骤由CH*→C* + H*变为CH4*→CH3* + H*。预吸附O能够显著降低甲烷脱氢的能垒,速率控制步骤均为CH4* + O*→CH3* + OH*,甲烷在团簇上O辅助脱氢的最高能垒的大小为Cu(111)(1.56 eV)>Pd6Cu(111)(1.44 eV)>Pd2Cu(111)(1.38 eV),Pd的添加对于直接脱氢和O辅助脱氢的性能都有所提升。
  • 图  1  三种催化剂模型的俯视图和侧视图(红球为Cu原子,蓝球为Pd原子)

    Figure  1  Top view and side view of three catalyst models ( Cu and Pd atom are shown as red and blue ball)

    图  2  CHx*(x=0–4)在催化剂表面的吸附构型(灰球代表C原子,白球代表H原子)

    Figure  2  Adsorption configuration of CHx*(x=0–4) over catalysts surface (C and H atom are shown as grey and white ball)

    图  3  甲烷在三个催化剂表面直接脱氢的过渡态构型

    Figure  3  Transition state configuration of direct dehydrogenation of methane over the surface of three catalysts

    图  4  O辅助甲烷脱氢在三个催化剂表面的过渡态构型(灰球、白球和红球分别代表C、H以及O原子)

    Figure  4  Transition state configuration of O-assisted methane dehydrogenation over the three catalyst surfaces(C, H and O atom are shown as grey, white and red ball)

    图  5  甲烷直接脱氢以及O辅助脱氢的能量曲线((a) Cu(111);(b) Pd2Cu(111);(c) Pd6Cu(111))

    Figure  5  Energy landscape of methane direct dehydrogenation and O-assisted dehydrogenation ((a) Cu(111); (b) Pd2Cu(111); (c) Pd6Cu(111))

    图  6  O辅助脱氢在Cu(111)、Pd2Cu(111)及Pd6Cu(111)催化剂上的能垒

    Figure  6  Energy barrier of O-assisted dehydrogenation on Cu(111), Pd2Cu(111) and Pd6Cu(111) clusters

    图  7  Cu(111)、Pd2Cu(111)和Pd6Cu(111)的d带态密度(DOS)

    Figure  7  d-band density of states for Cu(111), Pd2Cu(111) and Pd6Cu(111) (The red vertical lines represent the central position of the d-state PDOS, the blue lines represent the Fermi level EF)

    表  1  CHx*(x=0–4)在三种催化剂表面的吸附位点(site)和吸附能(energy)(eV)

    Table  1  Adsorption sites and adsorption energy (eV) of CHx*(x=0–4) over the surface of three catalysts

    SpeciesCu(111) Pd2Cu(111) Pd6Cu(111)
    siteenergysiteenergysiteenergy
    CH4*top−0.02 top−0.03 top−0.02
    CH3*hollow−0.98top−1.41top−1.12
    CH2*bridge−2.79hollow−3.13hollow−2.93
    CH*hollow−4.08hollow−4.65hollow−4.51
    C*hollow−4.54hollow−5.11hollow−5.17
    下载: 导出CSV

    表  2  甲烷在三个催化剂上直接脱氢的能垒和反应热(eV)

    Table  2  Energy barrier and heat of methane direct dehydrogenation on three catalysts (eV)

    Elementary stepCu(111) Pd2Cu(111) Pd6Cu(111)
    barrierheatbarrierheatbarrierheat
    CH4*→CH3* + H*1.801.40 2.431.19 2.431.46
    CH3*→CH2* + H*2.071.531.771.152.001.31
    CH2*→CH* + H*1.881.241.670.771.820.94
    CH*→C* + H*2.561.881.981.152.271.37
    下载: 导出CSV

    表  3  O辅助甲烷脱氢在三个催化剂表面上的能垒和反应热

    Table  3  Energy barrier and heat of reaction of O-assisted methane dehydrogenation over three catalyst surfaces

    Elementary stepCu(111)Pd2Cu(111)Pd6Cu(111)
    barrierheatbarrierheatbarrierheat
    CH4* + O* → CH3* + OH* 1.56 0.45 1.38 0.25 1.44 0.32
    CH3* + O*→ CH2* + OH* 0.64 −0.79 0.66 −0.09 0.80 −0.18
    CH2* + O*→ CH* + OH* 0.71 −0.41 0.44 −0.13 0.66 −0.27
    CH* + O*→ C* + OH* 0.83 −0.26 0.90 0.24 1.02 −0.09
    下载: 导出CSV
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  • 收稿日期:  2022-11-11
  • 录用日期:  2022-12-05
  • 修回日期:  2022-11-30
  • 网络出版日期:  2022-12-26

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