Influence of H2O on the adsorption of SO2 on CaO (001) surface: A DFT study
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摘要: 采用密度泛函理论研究了H2O对SO2在CaO（001）表面上吸附的影响。结果表明，以四种形式（-H2O、-H、-OH和-H&-OH）存在的H2O使SO2在CaO表面上的吸附构型发生改变。SO2在不同形式H2O基团邻位吸附时，-H使S原子的p轨道态密度峰明显左移且吸附能比洁净表面大90 kJ/mol，其余基团表面吸附能无明显变化；SO2吸附于-OH和-H&-OH生成HSO3基团，吸附能相比于洁净表面较小，可能作为暂态结构；SO2吸附于-H2O生成SO3基团，H2O断键生成的H基团起主要吸附作用，CaO表面上生成类似Ca（OH）2的局部结构且吸附能比洁净表面大45 kJ/mol。
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关键词:
- 密度泛函理论 /
- H2O /
- SO2 /
- CaO(001)表面 /
- 吸附
Abstract: The influence of H2O on the adsorption of SO2 on CaO (001) surface was investigated by density functional theory (DFT). The results indicate that H2O can have an effect on the adsorption geometries for SO2 on the CaO (001) surface. When SO2 is adsorbed to the CaO surface near a water group of different forms (viz., -H2O, -H, -OH and -H & -OH), the H group makes the adsorption energy 90 kJ/mol higher with the sulfur p-orbital shifting downward, whereas other groups have little effect on the adsorption energy. When SO2 is adsorbs to the -OH surface and -H & -OH surface, bisulfite-like structures are formed, with lower adsorption energies and tending to form more stable structures as intermediates. When SO2 adsorbs to the -H2O surface, bisulfite-like structure is formed and the H2O group decomposes to Ca(OH)2 like-structure on the CaO surface; the new H groups mainly bond the bisulfite and make adsorption energy 45 kJ/mol higher.-
Key words:
- density functional theory /
- H2O /
- SO2 /
- CaO(001) surface /
- adsorption
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图 1 SO2在洁净CaO表面上吸附构型及电子密度图
Figure 1 Structure and electron density maps of SO2 adsorbed on clean CaO surfaces (red: O atom; yellow: S atom; green: Ca atom)
图 2 H2O在洁净CaO表面上吸附构型及电子密度图(白色原子为H原子, 下同)
Figure 2 Structure and electron density maps of H2O adsorbed on clean CaO surfaces (white, H atom)
图 4 SO2在H2O上吸附构型(构型4)及电子密度图
Figure 4 Structure and electron density map of SO2 adsorbed to the H2O group
图 6 SO2在-H & -OH基团上吸附构型及电子密度图
Figure 6 Structure and electron density maps of SO2 adsorbed to the -H & -OH groups
图 8 SO2在-H表面上吸附构型及电子密度图
Figure 8 Structures and electron density maps of SO2 adsorbed to the -H surfaces
图 9 SO2分子在不同表面吸附态密度分布图
Figure 9 Density of state plots for SO2 adsorbed on different surfaces
(a): clean CaO surface; (b):-H2O surface; (c)-H surface
表 1 SO2在不同CaO表面吸附构型成键参数及电荷转移
Table 1 Adsorption energy, S-O bond distance, O-S-O bond angel, S-Osurf distance and charge transfer to SO2 for SO2 adsorption on different CaO surfaces
Structure Adsorption energy /(kJ·mol-1) S-O bond distance /nm O-S-O bond angle /(°) S-Osurf distance /nm Charge transfer to SO2 (e) 1-a 163.99 0.152 111.00 0.172 -0.27 1-b 172.08 0.150 111.00 0.169 -0.26 3-a 157.34 0.198 140.75 0.212 -0.27 3-b 147.99 0.150 110.78 0.174 -0.27 3-c 159.34 0.151 110.53 0.168 -0.27 5-a 165.43 0.151 110.58 0.167 -0.27 5-b 170.02 0.150 110.16 0.171 -0.27 7-a 160.62 0.150 110.44 0.168 -0.26 7-b 156.66 0.150 110.44 0.171 -0.26 8-a 259.92 0.154 110.36 - -0.66 8-b 252.14 0.153 112.72 - -0.67 8-c 229.63 0.153 111.80 0.299 -0.67 8-d 251.95 0.154 112.14 - -0.67 
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表 2 不同情况吸附构型化学键布居数对比
Table 2 Bond populations for SO2 adsorption on different surfaces
Structure Bond Population Bond distance Atomic position SO2 molecule O1-S1 0.33 1.44 O2-S1 0.33 1.44 SO2 adsorbing on clean CaO surfaces (1-a) O1-S1 0.39 1.50 O1, O2 from SO 2，O3 from CaO surface O2-S1 0.39 1.50 O3-S1 0.19 1.71 SO2 adsorbing on -H2O surface (4) H1-O4 0.48 0.98 O4 and O5 from CaO surface, O3 from H2O, O1 and O2 from SO2 H2-O5 0.59 0.98 O1-S1 0.46 1.46 O2-S1 0.33 1.50 O3-S1 0.11 1.85 SO2 adsorbing on -OH surface (7-c) O3-S1 0.48 0.99 O1 from OH group，O2 and O3 from SO2 O3-S1 0.45 1.47 O2-S1 0.37 1.50 O1- S1 0.13 1.81 O2-Ca1 0.11 2.42
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