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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Mechanism of C-C and C-H bond cleavage in ethanol oxidation reaction on Cu2O(111): a DFT-D and DFT plus U study
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Mechanism of C-C and C-H bond cleavage in ethanol oxidation reaction on Cu2O(111): a DFT-D and DFT plus U study

机译：C-C和C-H键切割在Cu2O（111）上乙醇氧化反应中的机制（111）：DFT-D和DFT加上U研究

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摘要

The performance of transition metal catalysts for ethanol oxidation reaction (EOR) in direct ethanol fuel cells (DEFCs) may be greatly affected by their oxidation. However, the specific effect and catalytic mechanism for EOR of transition metal oxides are still unclear and deserve in-depth exploitation. Copper as a potential anode catalyst can be easily oxidized in air. Thus, in this study, we investigated C-C and C-H bond cleavage reactions of CHxCO (x = 1, 2, 3) species in EOR on Cu2O(111) using PBE+U calculations, as well as the specific effect of +U correction on the process of adsorption and reaction on Cu2O(111). It was revealed that the catalytic performance of Cu2O(111) for EOR was restrained compared with that of Cu(100). Except for the C-H cleavage of CH2CO, all the reaction barriers for C-C and C-H cleavage were higher than those on Cu(100). The most probable pathway for CH3CO to CHCO on Cu2O(111) was the continuous dehydrogenation reaction. Besides, the barrier for C-C bond cleavage increased due to the loss of H atoms in the intermediate. Moreover, by the comparison of the traditional GGA/PBE method and the PBE+ U method, it could be concluded that C-C cleavage barriers would be underestimated without +U correction, while C-H cleavage barriers would be overestimated. +U correction was proved to be necessary, and the reaction barriers and the values of the Hubbard U parameter had a proper linear relationship.
机译：直接乙醇燃料电池（DEFC）中乙醇氧化反应（EOR）的过渡金属催化剂的性能可能极大地受其氧化的影响。然而，过渡金属氧化物EOR的特定效果和催化机制仍然不清楚并应得的深入剥削。作为潜在的阳极催化剂的铜可以容易地在空气中氧化。因此，在本研究中，我们使用PBE + U计算研究了CC和CH键在CU 2 O（111）上的EOR上的CC和CH键切割反应，以及+ U校正的特定效果Cu2O（111）上吸附和反应的方法。揭示了与Cu（100）的Cu2O（111）的浓度的Cu2O（111）的催化性能。除了CH2CO的C-H裂解外，C-C和C-H裂解的所有反应屏障高于Cu（100）的反应屏障。 CH3CO在CU 2 O（111）上的CH3CO至CHCO最可能的途径是连续的脱氢反应。此外，由于中间体中的H原子损失，C-C键裂解的屏障增加。此外，通过对传统的GGA / PBE方法和PBE + U方法的比较，可以得出结论，C-C裂解屏障不会被误入+ U校正，而C-H裂解屏障将被过高曝光。 + U校正被证明是必要的，并且反应屏障和哈伯德U参数的值具有适当的线性关系。

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    Xu Han; Miao Bei; Zhang Minhua; Chen Yifei; Wang Lichang;

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    Tianjin Univ Key Lab Minist Educ Green Chem Technol Tianjin 300072 Peoples R China;

    Tianjin Univ Key Lab Minist Educ Green Chem Technol Tianjin 300072 Peoples R China;

    Tianjin Univ Key Lab Minist Educ Green Chem Technol Tianjin 300072 Peoples R China;

    Tianjin Univ Key Lab Minist Educ Green Chem Technol Tianjin 300072 Peoples R China;

    Tianjin Univ Key Lab Minist Educ Green Chem Technol Tianjin 300072 Peoples R China;

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  • 正文语种 eng
  • 中图分类 物理学;化学;
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