不同价态金属掺杂对La<sub>2</sub>O<sub>3</sub>(001)表面上甲烷活化影响的研究

ZHANG Jia-yu; SUN Na; LING Li-xia; ZHANG Ri-guang; JIA Li-tao; LI De-bao; WANG Bao-jun

doi:10.1016/S1872-5813(23)60343-3

不同价态金属掺杂对La₂O₃(001)表面上甲烷活化影响的研究

doi: 10.1016/S1872-5813(23)60343-3

张家宇^{1, 2,},
孙娜^{1, 2,},
凌丽霞^{1, 3, ,},
章日光^2,,
贾丽涛^4,,
李德宝^4,,
王宝俊^{1, 2, 3, ,}

1.
太原理工大学化学工程与技术学院，山西太原 030024
2.
太原理工大学清洁高效煤利用国家重点实验室，山西太原 030024
3.
山西-浙大先进材料化工研究院，山西太原 030024
4.
中国科学院山西煤炭化学研究所煤转化国家重点实验室，山西太原 030024

详细信息

中图分类号: O643.3
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出版历程
- 收稿日期: 2022-10-23
- 修回日期: 2022-12-08
- 录用日期: 2022-12-15
- 网络出版日期: 2023-02-27
- 刊出日期: 2023-05-15

Effect of different valence metals doping on methane activation over La₂O₃(001) surface

ZHANG Jia-yu^{1, 2
,},
SUN Na^{1, 2
,},
LING Li-xia^{1, 3
, ,},
ZHANG Ri-guang^2
,,
JIA Li-tao^4
,,
LI De-bao^4
,,
WANG Bao-jun^{1, 2, 3
, ,}

1.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
2.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
3.
Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030024, China
4.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by the National Key R&D Program of China (2021YFA1502804), Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2022SX-FR001), the Key Projects of National Natural Science Foundation of China (21736007), and the Natural Science Foundation of Shanxi Province (20210302123094)

More Information

Corresponding author: E-mail: linglixia@tyut.edu.cn; wangbaojun@tyut.edu.cn

摘要

摘要: La₂O₃因具有优异的稳定性和较高的C₂烃选择性，因此，常被用于催化甲烷氧化偶联反应，而较差的甲烷解离活性却限制了其广泛应用。为了提高镧基催化剂活化甲烷的性能，将不同价态的金属掺杂在La₂O₃(001)表面，并采用密度泛函理论方法对CH₄在催化剂表面的活化行为进行了研究。结果表明，低价态金属(Li、Na、K、Mg、Ca、Sr和Ba)和等价态金属(Al、Ga、In)的掺杂可以显著提高La₂O₃(001)表面的CH₄解离活性。其中，CH₄在Li-La₂O₃(001)表面解离的活化能最低，仅为13.0 kJ/mol。而高价态金属(Zr、Nb、Re和W)掺杂不能提高La₂O₃(001)表面的CH₄解离活性。此外，通过研究催化剂表面氧空位形成能、酸碱性与CH₄解离活化能之间的关系发现，随着掺杂金属价态的增加，氧空位形成能也逐渐增大，而CH₄的解离活性呈现出降低趋势；碱金属和碱土金属的掺杂增大了催化剂表面的碱性，且碱金属掺杂的碱性强于碱土金属，同时，较强的碱性也表现出较高的CH₄转化活性。本研究对提高La₂O₃催化剂的甲烷转化活性具有指导意义。
- 甲烷 /
- La₂O₃催化剂 /
- 金属掺杂 /
- 活性 /
- 密度泛函理论
Abstract: La₂O₃ as a catalyst is used for oxidative coupling of methane (OCM) reactions due to its excellent stability and high C₂ selectivity, but poor activity on methane dissociation limits its wide application. Different valence metals are doped on the La₂O₃(001) surface to improve the methane conversion activity, and the activation of methane on metal-doped La₂O₃(001) surfaces has been investigated via the density functional theory (DFT) calculations. The relationship between the valence states of doped metals and the methane conversion activities shows that doping low valence metals (Li, Na, K, Mg, Ca, Sr and Ba) and equivalent metals (Al, Ga, In) can significantly improve the conversion activity of methane. Among them, the activation energy of methane on the Li-La₂O₃(001) surface is the lowest, which is only 13.0 kJ/mol. However, doping of high valence metals (Zr, Nb, Re and W) cannot improve the CH₄ dissociation activity. Furthermore, the relationships between surface oxygen vacancy formation energies, acid-base properties and the activation energies of CH₄ have also been investigated. The results show that with the increase of metal valence state, the oxygen vacancy formation energy increases, while the dissociation activity of CH₄ decreases. The introduction of alkali and alkaline earth metals increases the alkalinity of La₂O₃(001) surface, and the alkalinity of La₂O₃(001) doped with the alkali metal is stronger than that with the alkaline earth metal, exhibiting higher dissociation activity of CH₄. Our research may provide a guide for improving methane conversion activity on La₂O₃ catalysts.
- methane /
- La₂O₃ catalyst /
- metal doping /
- activity /
- density functional theory

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FIG. 2297. FIG. 2297.

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Figure 1 Top and side views of the slab model of the M-La₂O₃(001) surface Purple, blue and red balls denote the doped metal, La and O atoms, respectively

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Figure 2 Calculated binding energies of different valence metals doped on the La₂O₃(001) surface

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Figure 3 Calculated structures of the initial, transition and final states of CH₄ activation on the M-La₂O₃(001) (M = Li, Na, K, Mg, Ca, Sr and Ba) surfaces (top view) (the unit of bond length is Å)

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Figure 4 Calculated structures of the initial states, transition states and final states of CH₄ activation on the M-La₂O₃(001) (M = Al, Ga, In, Zr, Nb, Re and W) surfaces (the unit of bond length is Å)

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Figure 5 Activation energies of methane on the M-La₂O₃(001) (M = Li, Na, K, Mg, Ca, Sr and Ba) and pure La₂O₃(001) surfaces

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Figure 6 Activation energies of methane on the M-La₂O₃(001) (M = Al, In and Ga) and pure La₂O₃(001) surfaces

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Figure 7 Oxygen vacancy formation energies of the threefold-coordinated and sixfold-coordinated lattice oxygen on the M-La₂O₃(001) (M = Li, Na, K, Mg, Ca, Sr and Ba) and pure La₂O₃(001) surfaces

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Figure 8 Vacancy formation energies of the threefold-coordinated and sixfold-coordinated lattice oxygen on the M-La₂O₃(001) (M = Al, Ga, In, Zr, Nb, Re and W) and pure La₂O₃(001) surfaces

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Figure 9 Correlations between the oxygen vacancy formation energies and activation energies of methane on the different doped La₂O₃(001) surfaces

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Figure 10 Effect of alkali metals and alkaline earth metals (Li, Na, K, Mg, Ca, Sr and Ba) doping on the activity of La₂O₃(001) toward methane activation

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Table 1 Calculated energetics of CH₄ activation on the M-La₂O₃(001) (M = Li, Na, K, Mg, Ca, Sr and Ba) surfaces

Catalyst	E/(kJ·mol⁻¹)
Catalyst	E_ads(CH₄)	E_a	ΔE_r
Li-La₂O₃(001)	−4.4	13.0	−28.9
Na-La₂O₃(001)	−4.7	29.8	−21.2
K-La₂O₃(001)	−3.6	23.9	−27.8
Mg-La₂O₃(001)	−3.8	38.8	−3.3
Ca-La₂O₃(001)	−3.9	43.2	−15.5
Sr-La₂O₃(001)	−3.7	33.9	−16.4
Ba-La₂O₃(001)	−3.3	48.9	−11.5

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Table 2 Calculated energetics of methane activation on the La₂O₃(001) surfaces doped with equivalent and high valence metals, including CH₄ adsorption energy (E_ads), activation energy (E_a), and reaction heat (ΔE_r)

Catalyst	E/(kJ·mol⁻¹)
Catalyst	E_ads(CH₄)	E_a	ΔE_r
Al-La₂O₃(001)	−3.3	111.0	39.5
Ga-La₂O₃(001)	−3.3	125.7	20.4
In-La₂O₃(001)	−2.9	116.6	10.1
Zr-La₂O₃(001)	−2.5	162.1	147.2
Nb-La₂O₃(001)	−3.3	205.5	153.9
Re-La₂O₃(001)	−4.3	233.4	151.0
W-La₂O₃(001)	−4.3	180.7	104.9

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