Adsorption and selective hydrogenation mechanism of cinnamaldehyde on Pt(111) surface and Pt14 cluster
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摘要: 利用密度泛函理论研究了Pt（111）面及Pt14团簇对肉桂醛（CAL）的吸附作用和不完全加氢的反应机理。分析吸附能结果表明，肉桂醛分子以C=O与C=C键协同吸附在Pt（111）面上的六角密积（Hcp）位最稳定，以C=C键吸附在Pt14团簇上最稳定，且在Pt14团簇上的吸附作用较Pt（111）面更强。由过渡态搜索并计算得到的反应能垒及反应热可知，肉桂醛在Pt（111）面和Pt14团簇上均较容易对C=O键加氢得到肉桂醇（COL）。其中，优先加氢O原子为最佳反应路径，即Pt无论是平板还是团簇对肉桂醛加氢均有较好的选择性。同时发现，肉桂醛分子在Pt（111）面的加氢反应能垒较Pt14团簇上更低，即Pt的催化活性及对肉桂醛加氢产物选择性与其结构密切相关，其中，Pt（111）面对生成肉桂醇更加有利。Abstract: The adsorption and the mechanism for selective hydrogenation of cinnamaldehyde (CAL) on Pt (111) surface and Pt14 cluster were investigated by using density functional theory (DFT). The results illustrate that the synergistic adsorption of CAL molecule on Pt (111) surface with C=O and C=C bonds is most stable at the Hcp position, whereas most stable adsorption of CAL appears on the Pt14 cluster with C=C bond; the adsorption of CAL on the Pt14 cluster is stronger than that on Pt(111) surface. The reaction barriers for each elementary reaction were determined from the transition state search and the results suggest that CAL was preferentially hydrogenated at C=O on the Pt(111) surface and Pt14 cluster, forming cinnamyl alcohol (COL); the hydrogenation of O atom takes the priority. Both Pt plate and cluster have good selectivity for hydrogenation of CAL to COL. The reaction barrier of CAL hydrogenation on Pt(111) surface is lower than that on Pt14 cluster, indicating that the catalytic activity and selectivity of CAL hydrogenation are closely related to the structure of Pt catalysts; Pt(111) surface is more favorable for catalyzing the hydrogenation of CAL to COL.
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Key words:
- cinnamaldehyde /
- adsorption /
- hydrogenation /
- platinum /
- catalytic /
- density functional theory
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图 1 (a): Pt(111)面模型；(b): Pt14团簇模型；(c):肉桂醛分子模型
Figure 1 (a): Pt(111) surface model; (b): Pt14 cluster model; (c): CAL molecular model
图 2 肉桂醛在Pt(111)面和Pt14团簇上稳定吸附构型
Figure 2 Stable adsorption configuration of CAL on Pt(111) surface and Pt14 cluster
图 3 CAL与Pt(111)面和Pt14团簇吸附的态密度图
Figure 3 Partial densities of states (PDOS) and total densities of states (TDOS) of CAL adsorption on Pt(111) and Pt14
图 4 CAL吸附前后p轨道的分波态密度
Figure 4 p Oribital partial density of states of CAL before and after adsorption
图 6 各机理在Pt(111)和Pt14上的能量变化
Figure 6 Diagram for relative energy of reaction mechanisms on Pt(111) and Pt14
表 1 肉桂醛在Pt(111)面上不同吸附构型的吸附能
Table 1 Adsorption energy (Eads) of CAL molecule on Pt(111) surface
Adsorption mode Adsorption site Eads/(kJ·mol-1) Adsorption mode Adsorption site Eads /(kJ·mol-1) O Bri 92.02 C=O and C=C Bri-Bri 89.21 Fcc 91.49 Bri-Fcc 92.04 Hcp 91.39 Bri-Hcp 81.58 Top 91.62 Bri-Top 91.14 Fcc-Bri 89.40 C=C Bri 92.01 Fcc-Fcc 91.95 Fcc 90.42 Fcc-Hcp 91.18 Hcp 91.39 Fcc-Top 91.91 Top 91.92 Hcp-Bri 88.36 Hcp-Fcc 91.56 C=O Bri 74.08 Hcp-Hcp 92.42 Fcc 72.52 Hcp-Top 92.09 Hcp 67.65 Top-Bri 91.08 Top 91.16 Top-Fcc 90.71 Top-Hcp 90.86 Top-Top 90.84 
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表 2 Pt(111)和Pt14上CAL的Mulliken电荷布居数
Table 2 Mulliken charge populations of CAL molecule at advantage adsorption site on Pt(111) and Pt14
Atom Charge/e free CAL CAL-Pt(111) CAL-Pt14 O1 -0.384 -0.355 -0.336 C2 0.274 0.223 0.256 C3 -0.085 -0.117 -0.089 C4 0.019 -0.028 -0.037 C5 0.086 0.038 0.085 C6 -0.042 -0.069 -0.073 C7 -0.030 -0.075 -0.073 C8 -0.028 -0.073 -0.084 C9 -0.028 -0.073 -0.071 C10 -0.063 -0.083 -0.094 H11 -0.011 0.031 0.072 H12 0.045 0.098 0.132 H13 0.041 0.097 0.132 H14 0.037 0.096 0.087 H15 0.041 0.105 0.092 H16 0.042 0.108 0.090 H17 0.042 0.106 0.092 H18 0.044 0.099 0.088 Tol 0.000 0.128 0.269
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表 3 Pt(111)和Pt14上各基元反应的活化能和反应热
Table 3 Activation energy(Ea) and reaction energy(ΔE) of primitive reactions on Pt(111) and Pt14
Mechanism Reaction step CAL-Pt(111) CAL-Pt14 Ea /(kJ·mol-1) ΔE /(kJ·mol-1) Ea /(kJ·mol-1) ΔE /(kJ·mol-1) R12 r1 21.27 -43.04 86.63 33.83 r12 65.02 -12.70 53.29 23.66 R21 r2 136.75 71.60 228.91 102.78 r21 244.47 -127.67 92.99 -40.73 R34 r3 107.04 4.48 142.49 52.21 r34 129.80 -87.43 120.45 -62.27 R43 r4 224.32 -1.37 148.53 29.88 r43 24.28 -84.56 94.44 -37.25 R14 r1 21.27 -43.04 86.63 33.83 r14 228.88 -7.52 67.62 32.74 R41 r4 224.32 -1.37 148.53 29.88 r41 243.82 -43.38 88.45 42.42
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