甲胺和甲烷在不同催化剂表面裂解的密度泛函理论研究
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摘要
本文运用DFT–GGA方法及平板模型系统地研究了甲胺和甲烷在不同催化剂表面的裂解,通过研究它们在不同催化剂表面的反应活化能,揭示不同催化剂的活性差异。本文的研究获得了以下结论:
(1)研究了甲胺的C–N键裂解生成甲基和氨基这一反应过程中涉及到的物种甲胺、甲基和氨基在清洁的Mo(100)、C(N, O, P, Cl)原子改性的Mo(100)、Mo2C(100)、MoN(100)和Pt(100)表面的吸附,以及甲胺的C–N键在这些表面的裂解。结果表明,C、N、O、P原子改性的Mo(100)表面增加了C–N键裂解的活化能,即这些改性原子钝化了清洁的Mo(100)表面;而Cl原子改性的Mo(100)表面却略微降低了C–N键裂解的活化能。处于同一周期的C、N、O原子,当它们位于Mo(100)的表面层时,对Mo(100)表面钝化的程度相近。然而,当C原子处于Mo(100)表面的亚表面层时,却极大程度地提高了该表面的反应活性。在Mo2C(100)和MoN(100)表面,甲胺C–N键裂解的活化能高于在清洁的Mo(100)表面,表明C和N原子降低了Mo的表面活性。而甲胺的C–N键在Mo2C(100)和MoN(100)表面裂解的活化能与在Pt(100)表面相当,因此,Mo2C(100)和MoN(100)表面可以代替昂贵的Pt–族金属(如钌、铑、钯、锇、铱、铂)来催化甲胺的C–N键的裂解。
(2)研究了甲胺在Ni(111)、Ni(100)、台阶的Ni(111)和N原子改性的Ni(100) (N–Ni(100))表面可能的吸附裂解步骤。计算分析了裂解过程中可能出现的中间物种的吸附性质,详细研究了不同的催化剂对甲胺的第一步裂解,即C–H、N–H和C–N这三种原子键裂解的催化活性的差异。结果表明,这四种金属镍表面的活性降低的顺序依次为:台阶的Ni(111) > Ni(100) > Ni(111) > N–Ni(100),表明改性N原子的存在降低了Ni(100)表面的活性。对于所研究的三个裂解反应,在这四种表面,C–N键裂解的活化能最高;在Ni(111)和Ni(100)表面,C–H键裂解的活化能最低;而在台阶的Ni(111)和N–Ni(100)表面,N–H键裂解的活化能最低。
(3)研究了CH4的C–H键在Pd基催化剂表面裂解的能学过程。结果表明,在清洁的Pd表面,C–H键裂解的反应是一个结构敏感反应。与清洁的Pd表面相比,O原子改性的Pd表面升高了反应CH4+O→CH3+OH和CH4+O→CH3+H+O的活化能。并且在相同的Pd表面,反应CH4+O→CH3+OH的活化能随着改性O原子覆盖度的增加而升高。从活化能的计算结果可以看出,CH4的C–H键裂解生成甲基和羟基的反应在O原子改性的Pd表面、PdO(100)和PdO(110)表面是结构非敏感性的,而该反应又是甲烷催化燃烧反应中的速控反应,因此,CH4在Pd表面的催化燃烧反应是结构非敏感性反应,这与实际实验相符合。另外,亚表面层O原子的存在,降低了反应CH4+O→CH3+OH在表面层O原子改性的Pd(111)表面的活化能。
In this thesis, the decomposition mechanisms of methylamine and methane on some catalysts surfaces have been systematically investigated by DFT–GGA method and slab model. The reactivity difference of various catalysts surfaces has been studied by the calculation of activation energy. The main conclusions of this work are summarized as follow.
(1) The adsorption of methylamine, methyl, and amino involved in the C–N bond cleavage of methylamine and the dissociation of C–N bond have been investigated on the clean Mo(100), C(N, O, P, Cl) atom modified Mo(100), Mo2C(100), MoN(100), and Pt(100) surface. For C–N bond cleavage of methylamine, compared with that on the clean Mo(100), the calculated results show that the activation energy on the Mo(100) surface modified with the C, N, O, or P atom is increased. That is, the clean surface is deactivated by these modification atoms. Whereas the barrier on the Cl atom modified Mo(100) surface is slightly decreased. For the C, N, and O atom listed in the same row in the element period table, when they are on the surface of Mo(100), the passivation effect induced by them on the Mo(100) is almost the same. However, the carbon atom on the subsurface increases the reactivity of Mo(100) dramatically. On the Mo2C(100) and MoN(100) surface, the activation energy of the C–N bond cleavage is higher than that on clean Mo(100). This indicates that the presence of carbon and nitrogen decreased the reactivity of Mo(100). The barriers for the C–N bond breaking on Mo2C(100) and MoN(100) surface are similar to that on Pt(100), suggesting that the properties of the transition metal carbides and nitrides for the C–N bond scission of methylamine might be very similar to the expensive Pt-group metals (Ru, Rh, Pd, Os, Ir, Pt).
(2) As regards for methylamine decomposition on Ni(111), Ni(100), stepped Ni(111), and nitrogen atom modified Ni(100) (N–Ni(100)), the adsorption energies under the most stable configuration of the possible species and the reactivity difference of the catalysts to the C–H, N–H, and C–N bond breaking have been investigated. Through systematic calculations for the kinetics mechanism of methylamine decomposition on these surfaces, it is found that the reactivity of the four nickel surfaces decrease with the order of stepped Ni(111) > Ni(100) > Ni(111) > N–Ni(100) and the presence of nitrogen atom decreased the reactivity of Ni(100). The barrier for the C–N bond breaking is the highest on these four surfaces, the barrier for the C–H bond breaking is the lowest on Ni(111) and Ni(100), whereas the barrier for the N–H bond breaking is the lowest on stepped Ni(111) and N–Ni(100).
(3) The cleavage of the C–H bond in methane has been studied on the palladium based catalysts. The results show that such a reaction is a structure sensitive reaction on clean palladium surfaces. For the reaction CH4+O→CH3+OH and CH4+O→CH3+H+O, compared with that occurred on clean palladium surface, the barrier is increased. And on the same palladium surface, for the reaction CH4+O→CH3+OH, the activation energy increased with coverage. From the calculation results of activation energy, we can see that the C–H bond breaking of methane forming methyl hydroxyl is structure insensitive on the oxygen atom modified palladium, PdO(100), and PdO(110) surfaces. The reaction CH4+O→CH3+OH is the limiting step of the methane catalytic combusition. So, the catalytic combustion reaction of methane on palladium surfaces is a structure insensitive reaction, which verifies the experiment. In addition, for the reaction CH4+O→CH3+OH, the presence of subsurface oxygen decreased the barrier on oxygen atom modified Pd(111).
(1)研究了甲胺的C–N键裂解生成甲基和氨基这一反应过程中涉及到的物种甲胺、甲基和氨基在清洁的Mo(100)、C(N, O, P, Cl)原子改性的Mo(100)、Mo2C(100)、MoN(100)和Pt(100)表面的吸附,以及甲胺的C–N键在这些表面的裂解。结果表明,C、N、O、P原子改性的Mo(100)表面增加了C–N键裂解的活化能,即这些改性原子钝化了清洁的Mo(100)表面;而Cl原子改性的Mo(100)表面却略微降低了C–N键裂解的活化能。处于同一周期的C、N、O原子,当它们位于Mo(100)的表面层时,对Mo(100)表面钝化的程度相近。然而,当C原子处于Mo(100)表面的亚表面层时,却极大程度地提高了该表面的反应活性。在Mo2C(100)和MoN(100)表面,甲胺C–N键裂解的活化能高于在清洁的Mo(100)表面,表明C和N原子降低了Mo的表面活性。而甲胺的C–N键在Mo2C(100)和MoN(100)表面裂解的活化能与在Pt(100)表面相当,因此,Mo2C(100)和MoN(100)表面可以代替昂贵的Pt–族金属(如钌、铑、钯、锇、铱、铂)来催化甲胺的C–N键的裂解。
(2)研究了甲胺在Ni(111)、Ni(100)、台阶的Ni(111)和N原子改性的Ni(100) (N–Ni(100))表面可能的吸附裂解步骤。计算分析了裂解过程中可能出现的中间物种的吸附性质,详细研究了不同的催化剂对甲胺的第一步裂解,即C–H、N–H和C–N这三种原子键裂解的催化活性的差异。结果表明,这四种金属镍表面的活性降低的顺序依次为:台阶的Ni(111) > Ni(100) > Ni(111) > N–Ni(100),表明改性N原子的存在降低了Ni(100)表面的活性。对于所研究的三个裂解反应,在这四种表面,C–N键裂解的活化能最高;在Ni(111)和Ni(100)表面,C–H键裂解的活化能最低;而在台阶的Ni(111)和N–Ni(100)表面,N–H键裂解的活化能最低。
(3)研究了CH4的C–H键在Pd基催化剂表面裂解的能学过程。结果表明,在清洁的Pd表面,C–H键裂解的反应是一个结构敏感反应。与清洁的Pd表面相比,O原子改性的Pd表面升高了反应CH4+O→CH3+OH和CH4+O→CH3+H+O的活化能。并且在相同的Pd表面,反应CH4+O→CH3+OH的活化能随着改性O原子覆盖度的增加而升高。从活化能的计算结果可以看出,CH4的C–H键裂解生成甲基和羟基的反应在O原子改性的Pd表面、PdO(100)和PdO(110)表面是结构非敏感性的,而该反应又是甲烷催化燃烧反应中的速控反应,因此,CH4在Pd表面的催化燃烧反应是结构非敏感性反应,这与实际实验相符合。另外,亚表面层O原子的存在,降低了反应CH4+O→CH3+OH在表面层O原子改性的Pd(111)表面的活化能。
In this thesis, the decomposition mechanisms of methylamine and methane on some catalysts surfaces have been systematically investigated by DFT–GGA method and slab model. The reactivity difference of various catalysts surfaces has been studied by the calculation of activation energy. The main conclusions of this work are summarized as follow.
(1) The adsorption of methylamine, methyl, and amino involved in the C–N bond cleavage of methylamine and the dissociation of C–N bond have been investigated on the clean Mo(100), C(N, O, P, Cl) atom modified Mo(100), Mo2C(100), MoN(100), and Pt(100) surface. For C–N bond cleavage of methylamine, compared with that on the clean Mo(100), the calculated results show that the activation energy on the Mo(100) surface modified with the C, N, O, or P atom is increased. That is, the clean surface is deactivated by these modification atoms. Whereas the barrier on the Cl atom modified Mo(100) surface is slightly decreased. For the C, N, and O atom listed in the same row in the element period table, when they are on the surface of Mo(100), the passivation effect induced by them on the Mo(100) is almost the same. However, the carbon atom on the subsurface increases the reactivity of Mo(100) dramatically. On the Mo2C(100) and MoN(100) surface, the activation energy of the C–N bond cleavage is higher than that on clean Mo(100). This indicates that the presence of carbon and nitrogen decreased the reactivity of Mo(100). The barriers for the C–N bond breaking on Mo2C(100) and MoN(100) surface are similar to that on Pt(100), suggesting that the properties of the transition metal carbides and nitrides for the C–N bond scission of methylamine might be very similar to the expensive Pt-group metals (Ru, Rh, Pd, Os, Ir, Pt).
(2) As regards for methylamine decomposition on Ni(111), Ni(100), stepped Ni(111), and nitrogen atom modified Ni(100) (N–Ni(100)), the adsorption energies under the most stable configuration of the possible species and the reactivity difference of the catalysts to the C–H, N–H, and C–N bond breaking have been investigated. Through systematic calculations for the kinetics mechanism of methylamine decomposition on these surfaces, it is found that the reactivity of the four nickel surfaces decrease with the order of stepped Ni(111) > Ni(100) > Ni(111) > N–Ni(100) and the presence of nitrogen atom decreased the reactivity of Ni(100). The barrier for the C–N bond breaking is the highest on these four surfaces, the barrier for the C–H bond breaking is the lowest on Ni(111) and Ni(100), whereas the barrier for the N–H bond breaking is the lowest on stepped Ni(111) and N–Ni(100).
(3) The cleavage of the C–H bond in methane has been studied on the palladium based catalysts. The results show that such a reaction is a structure sensitive reaction on clean palladium surfaces. For the reaction CH4+O→CH3+OH and CH4+O→CH3+H+O, compared with that occurred on clean palladium surface, the barrier is increased. And on the same palladium surface, for the reaction CH4+O→CH3+OH, the activation energy increased with coverage. From the calculation results of activation energy, we can see that the C–H bond breaking of methane forming methyl hydroxyl is structure insensitive on the oxygen atom modified palladium, PdO(100), and PdO(110) surfaces. The reaction CH4+O→CH3+OH is the limiting step of the methane catalytic combusition. So, the catalytic combustion reaction of methane on palladium surfaces is a structure insensitive reaction, which verifies the experiment. In addition, for the reaction CH4+O→CH3+OH, the presence of subsurface oxygen decreased the barrier on oxygen atom modified Pd(111).
引文
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