Fe、La掺杂和氧缺陷对CeO2表面吸附As2O3的密度泛函理论研究

卢鲲鹏; 张凯华; 张锴

doi:10.19906/j.cnki.JFCT.2024005

Fe、La掺杂和氧缺陷对CeO₂表面吸附As₂O₃的密度泛函理论研究

doi: 10.19906/j.cnki.JFCT.2024005

华北电力大学热电生产过程污染物监测与控制北京市重点实验室, 北京 102206

基金项目: 国家自然科学基金委与山西煤基低碳联合基金重点项目（U1910215）和国家重点研发计划（2020YFB0606201）资助

详细信息

通讯作者:
E-mail: khzhang@ncepu.edu.cn

中图分类号: TK22
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出版历程
- 收稿日期: 2024-01-08
- 修回日期: 2024-02-05
- 录用日期: 2024-02-05
- 网络出版日期: 2024-03-13

Density functional theory study of adsorption of As₂O₃ on CeO₂ surface by Fe, La doping and oxygen defects

Beijing Key Laboratory of Emission Surveillance and Control for Thermal Power Generation, North China Electric Power University, Beijing 102206, China

Funds: The project was supported by the National Natural Science Foundation of China (U1910215) and the National Key R&D Program of China (2020YFB0606201).

摘要

摘要: 采用密度泛函理论研究了As₂O₃（g）在Fe、La掺杂CeO₂(110)表面及氧缺陷LaCeO(110)表面的吸附行为，探索了LaCeO表面砷吸附能力显著高于FeCeO表面的主要原因。结果表明，As₂O₃（g）的吸附效果与吸附位点数量、吸附能、键长和电荷转移密切相关。纯CeO₂表面的吸附主要为化学吸附，吸附能绝对值大于−4.22 eV，电荷转移量为−0.19− −0.31 e，As₂O₃得到电荷带负电，起表面受主作用，因此吸附量较小。FeCeO（110）表面新增Fe顶位和Bridge-2桥位两个吸附位，其中，Fe顶位为化学吸附，Fe掺杂改变了FeCeO表面电子分布和晶格结构，但并未改变As₂O₃与FeCeO之间的电荷转移方向，因此，As₂O₃仍呈负离子形式吸附。LaCeO（110）表面新增了三个吸附位：La顶位、Bridge-3桥位和Hollow-2空位，La掺杂改变了As₂O₃与LaCeO之间的电荷转移方向，使得As₂O₃失电子呈正离子吸附，起表面施主作用，因此，吸附能力增强。无O₂环境下，单一O缺陷LaCeO（110）表面吸附能力低于完整LaCeO表面；有O₂环境下，O缺陷有利于As₂O₃的吸附。
- 密度泛函理论 /
- 二氧化铈 /
- Fe、La掺杂 /
- As₂O₃吸附 /
- O缺陷
Abstract: Density functional theory (DFT) was used to study the adsorption behavior of As₂O₃ (g) on iron and lanthanum doped CeO₂ (110) and oxygen-deficient LaCeO (110) surfaces, and the reasons for the arsenic adsorption capacity of LaCeO surface was significantly higher than that of FeCeO surface was explored. The results show that the adsorption effect of As₂O₃ (g) is closely related to the number of adsorption sites, adsorption energy, bond length and charge transfer amount. Ce and O atoms on the surface of pure CeO₂ are both active sites, and the adsorption is mainly chemisorption, the absolute adsorption energy is greater than −4.22 eV, and the charge transfer amount is −0.19− −0.31 e. As₂O₃ has a negative charge and acts as a surface accepter, while CeO₂ loses electrons and has a positive charge on the surface, which acts as a surface donor. The number of free electrons in the CeO₂ conduction band gradually decreases, the conductivity decreases, and it is difficult to provide more electrons continuously, so the adsorption amount is small. Two adsorption sites are added on the surface of FeCeO (110): Fe top site and Bridge-2 Bridge site, where Fe top site is chemical adsorption and Bridge-2 Bridge site is physical adsorption. The gap doping of Fe changes the electron distribution and lattice structure on the surface of FeCeO, resulting in obvious deformation of the lattice and reducing the difficulty of bonding, thus increasing the configurational adsorption energy of some configurations. However, it does not change the charge transfer direction between As₂O₃ and FeCeO, thus not changing the surface adsorption form of As₂O₃. As₂O₃ is still adsorbed in the form of negative ions, which plays the role of surface acceptor, and the adsorption amount is small. LaCeO (110) has three new adsorption sites: La top site, Bridge-3 Bridge site and Hollow-2 vacancy, among which the La top site and Bridge-3 Bridge site are chemical adsorption. La doping changes the charge transfer direction between As₂O₃ and LaCeO, resulting in positive ion adsorption of As₂O₃ with electron loss and surface donor function. The electrons on the surface of LaCeO play the role of surface acceptor. With the progress of adsorption, the number of free electrons in the conduction band increases, and the conductivity increases. Therefore, the adsorption capacity of As₂O₃ on the surface of LaCeO increases. In the absence of O₂, the number of chemical bonds and bond energy formed on the surface of LaCeO (110) with single O defect are smaller than those on the surface of LaCeO, and the charge transfer on the surface of the defect is less, so the adsorption energy decreases. In this case, As₂O₃ obtains electrons and acts as the surface donor, and the adsorption capacity is lower than that on the complete LaCeO surface. In the presence of O₂, the adsorption energy and charge transfer number increase in the ortho-configuration after O₂ supplementation with O defect. As₂O₃ is positively adsorbed in ionic form, and the adsorption energy is also higher than that on the intact LaCeO surface. The adsorption capacity of As₂O₃ is better than that on the LaCeO surface, indicating that O defect is conducive to the adsorption of As₂O₃ in the presence of O₂.
- density functional theory /
- CeO₂ /
- Fe、La doping /
- As₂O₃ adsorption /
- oxygen deficiency

HTML全文

图 1 As₂O₃和CeO₂结构模型示意图

Figure 1 Structural model of As₂O₃ and CeO₂ ((a), (b), and (c) represent As₂O₃ front view, CeO₂ side view, and CeO₂ top view respectively.)

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图 2 As₂O₃在CeO₂表面的吸附

Figure 2 Adsorption of As₂O₃ on CeO₂ surface

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图 3 1B构型分波态密度

Figure 3 1B Configurational fractal density

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图 4 1B构型电荷转移情况

Figure 4 1B Configuration charge transfer

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图 5 Fe原子的两种掺杂形式

Figure 5 Two doping forms of Fe atoms ((a) and (b) are the top view and side view of gap doping, and (c) and (d) are the top view and side view of alternative doping).

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图 6 2B、2C、2D构型结构图

Figure 6 2B, 2C, 2D structure diagram

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图 7 2B构型差分电荷密度分布

Figure 7 2B configuration differential charge density distribution

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图 8 La原子的两种掺杂形式

Figure 8 Two doping forms of La atoms

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图 9 3B、3F、3H构型结构图

Figure 9 3B, 3F, 3H structure diagram

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图 10 3B构型分波态密度

Figure 10 3B Configurational fractal density

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图 11 3B构型电荷转移情况

Figure 11 3B Configuration charge transfer

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图 12 单原子氧缺陷La掺杂CeO₂（110）表面

Figure 12 Single atomic oxygen defect La doped CeO₂(110) surface

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图 13 4A、4B、4C构型结构图

Figure 13 4A, 4B, 4C structure diagram

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图 14 4A*、4B*、4C*构型结构图

Figure 14 4A*, 4B*, 4C* structure diagram

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图 15 4B*构型分波态密度

Figure 15 4B* Configurational fractal density

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表 1 As₂O₃分子在CeO₂（110）表面的吸附能、键长和电荷转移

Table 1 Adsorption energy, bond length and charge transfer of As₂O₃ molecules on CeO₂ (110) surface

	Adsorption structure（X-Y）	E_ad/eV	R_As-O/Å	R_Ce-Oads/Å	ΔQ/e
1A	O2-O5	−5.89	1.90	2.33	−0.28
1B	As1-O5	−7.42	1.84	2.31	−0.22
1C	O2-Ce1	−6.82	1.87	2.26	−0.29
1D	As1-Ce1	−6.60	1,87	2.24	−0.28
1F	02-Bridge-1	−5.57	1,92	2.35	−0.31
1E	As1-Bridge-1	−0.04	4.41	4.97	−0.04
1G	02-Hollow1	−4.22	1.82	2.38	−0.19
1H	As1-Hollow1	−0.06	4.41	4.39	−0.06

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表 2 As₂O₃分子在FeCeO（110）表面的吸附能、键长和电荷转移

Table 2 Adsorption energy, bond length and charge transfer of As₂O₃ molecules on FeCeO (110) surface

	Adsorption structure（X-Y）	E_ad/eV	R_As-O/Å	R_Ce-Oads/Å	ΔQ/e
2A	O2-O5	−6.55	1.85	4.31	−0.20
2B	As1-O5	−8.02	1.84	2.27	−0.14
2C	O2-Ce1	−8.56	1.82	2.06	−0.22
2D	As1-Ce1	−0.22	4.03	4.58	−0.05
2E	O2-Fe	−2.54	1.82	2.45	−0.2
2F	As1-Fe	−4.42	1.93	2.29	−0.32
2G	O2- Bridge-1	−8.29	1.82	2.27	−0.23
2H	As1- Bridge-1	1.51	4.08	4.78	−0.06
2I	O2-Bridge-2	0.26	2.98	4.42	−0.05
2J	As- Bridge-2	0.31	2.95	2.51	−0.07

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表 3 As₂O₃分子在LaCeO（110）表面的吸附能、键长和电荷转移

Table 3 Adsorption energy, bond length and charge transfer of As₂O₃ molecules on LaCeO (110) surface

	Adsorption structure (X-Y)	E_ad/eV	R_As-O/Å	R_Ce-Oads/Å	ΔQ/e
3A	O2-O5	−7.74	1.91	2.36	0.36
3B	As1-O5	−10.83	1.78	2.42	0.46
3C	O2-Ce1	−11.09	1.78	2.51	0.45
3D	As1-Ce1	−10.13	1.91	4.76	0.35
3E	O2-La	−0.81	2.66	6.12	−0.04
3F	As1-La	−8.44	1.89	2.52	0.37
3G	O2- Bridge-1	−8.56	1.88	2.43	0.39
3H	As1- Bridge-1	−9.31	1.91	2.36	0.35
3I	O2- Bridge-3	−12.53	1.79	2.60	0.37
3J	As1- Bridge-3	−10.70	1.88	2.43	0.36
3K	02-Hollow-1	−11.81	1.79	2.51	0.46
3L	As1-Hollow-1	−11.82	1.81	2.51	0.43
3M	02-Hollow-2	−10.29	1.91	3.87	0.36
3N	As1-Hollow-2	−0.08	4.20	5.12	−0.04

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表 4 As₂O₃分子在LaCeO（O_v）（110）表面的吸附能、键长和电荷转移

Table 4 Adsorption energy, bond length and charge transfer of As₂O₃ molecules on LaCeO(O_v) (110) surface

	Adsorption structure	E_ad	R_As-O/Å	R_Ce-Oads/Å	ΔQ/e
4A	As1-O_4v	−5.53	1.76	2.50	−0.12
4B	As1-O4(O_7v)	−5.59	1.86	2.36	−0.24
4C	O2−O4(O_7v)	−6.50	1.98	4.85	−0.30

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表 5 As₂O₃分子在LaCeO（O₂）（110）表面的吸附能、键长和电荷转移

Table 5 Adsorption energy, bond length and charge transfer of As₂O₃ molecules on LaCeO(O₂) (110) surface

	Adsorption structure	E_ad	R_As-O/Å	R_Ce-Oads/Å	ΔQ/e
4A*	As1- O_4v（O₂）	−2.28	1.76	2.50	−0.25
4B*	As1-O4(O_7v-O₂)	−10.95	1.80	2.47	0.52
4C*	O2-O4(O_7v-O₂)	−11.50	1.78	2.91	0.44

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