Fe<sub>3</sub>O<sub>4</sub>(001)-B表面水煤气变换反应机理第一性原理研究

孟宇; 刘小艳; 陈娟; 马亚军; 赵姝

Fe₃O₄(001)-B表面水煤气变换反应机理第一性原理研究

孟宇^{1, 2, ,},
刘小艳¹,
陈娟¹,
马亚军¹,
赵姝³

1.
榆林学院陕西省低变质煤洁净利用重点实验室, 陕西榆林 719000
2.
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 030001
3.
北京工业大学材料学院, 北京 100124

基金项目:

陕西省自然科学基础研究计划资助项目 2019JQ-905

陕西省自然科学基础研究计划资助项目 2018JZ2004

陕西省教育厅科研计划项目资助 19JS071

榆林市2019年科技计划项目 2019-83-1

榆林学院博士科研启动基金 17GK12

榆林学院博士科研启动基金 17GK13

煤转化国家重点实验室开放课题基金 J20-21-908

详细信息

通讯作者:
孟宇Tel; 15529967677. E-mail:mengyu@yulinu.edu.cn

中图分类号: O643.32
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- 文章访问数: 220
- HTML全文浏览量: 102
- PDF下载量: 17
- 被引次数: 0
出版历程
- 收稿日期: 2020-02-20
- 修回日期: 2020-04-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-05-10

First-principle study on the reaction mechanism of water-gas shift on the Fe₃O₄ (001)-B surface

MENG Yu^{1, 2
, ,},
LIU Xiao-yan¹,
CHEN Juan¹,
MA Ya-jun¹,
ZHAO Shu³

1.
Shaanxi Key Laboratory of Low Metamorphic Coal Clean Utilization, Yulin University, Yulin 719000, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
School of Materials, Beijing University of Technology, Beijing 100124, China

Funds:

Natural Science Foundation Research Program of Shaanxi Province 2019JQ-905

Natural Science Foundation Research Program of Shaanxi Province 2018JZ2004

Scientific Research Program Funded by Shaanxi Provincial Education Department 19JS071

Scientific Research Program Funded by Yulin Government 2019-83-1

PhD Research Startup Foundation of Yulin University 17GK12

PhD Research Startup Foundation of Yulin University 17GK13

the Foundation of State Key Laboratory of Coal Conversion J20-21-908

摘要

摘要: 采用自旋极化的密度泛函理论方法系统地研究了Fe₃O₄（001）-B表面水煤气变换的反应机理，计算了整个反应历程。结果表明，对于Fe₃O₄（001）-B表面上的水煤气变换反应，氧化还原、联合和再生三种反应路径共存，但氧化还原和联合机理的有效能垒较低，因而更占优势。对于生成H₂的基元反应，其活性受表面H浓度和催化剂表面O缺陷浓度影响；较高的表面H浓度和O缺陷浓度均有利于H₂生成。这些结果有助于进一步认识铁氧催化剂上的水煤气变换反应机理。
- 水煤气变换反应 /
- Fe₃O₄ (001)-B表面 /
- 反应机理 /
- 第一性原理
Abstract: The reaction mechanism of water-gas shift (WGS) on the Fe₃O₄ (001)-B surface was systematically studied by using the density functional theory (DFT) calculation with spin polarization. The results show that for the WGS on the Fe₃O₄ (001)-B surface, three reaction routes including redox, association and regeneration ones coexist, though the redox and association routes may be more important with much lower effective energy barriers. The elementary reaction of H₂ formation is influenced by the concentrations of surface H and O defects; higher concentrations of H species and O defects on the catalyst surface are beneficial to the formation of H₂. These results should be helpful for a better understanding of the WGS reaction mechanism on the iron-oxygen catalyst.
- water-gas shift reaction /
- Fe₃O₄ (001)-B /
- reaction mechanism /
- first principle

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图 1 Fe₃O₄ (001)-B表面结构模型

(a): top view; (b): side view

Figure 1 Fe₃O₄ (001)-B surface model of represented Fe-based catalyst

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图 2 吸附的H₂O、CO、CO₂和H₂的最稳定构型及吸附能

(red ball for surface O, pink ball for O of H₂O or CO₂, light-blue ball for subsurface Fe, black-blue ball for surface Fe, white ball for H, black ball for C)

Figure 2 Most stable adsorption structures and adsorption energies (eV) of H₂, CO, CO₂ and H₂ on Fe₃O₄ (001)-B surface

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图 3 H₂O在Fe₃O₄ (001)-B表面的直接解离和OH的辅助解离过程的构型及对应能量

Figure 3 Structures and energies of direct dissociation of H₂O to O^* + 2H^* and 2^*OH to ^*H₂O and ^*O

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图 4 CO₂在Fe₃O₄ (001)-B表面生成的不同机理过程对应的构型及势能面能量

Figure 4 Structures and energies of CO₂ formation step for three reaction routes

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图 5 CO₂在Fe₃O₄ (001)-B表面生成的不同机理势能面比较

Figure 5 Potential energy surface comparison of CO₂ formation step for three reaction routes

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图 6 表面吸附的H在Fe₃O₄ (001)-B表面迁移过程的结构和对应能量

Figure 6 Structures and energies of H transfer step on Fe₃O₄ (001)-B surface

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图 7 表面吸附的H在Fe₃O₄ (001)-B表面迁移过程的势能面

Figure 7 Potential energy surface of H transfer step on Fe₃O₄ (001)-B surface

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图 8 H₂在高低覆盖度下在Fe₃O₄ (001)-B表面生成反应历程的结构和对应能量

Figure 8 Structures and corresponding energies of H₂ formation step on Fe₃O₄ (001)-B at two converges

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图 9 H与Fe₃O₄ (001)-B表面不同位点作用后的电子态密度分布

Figure 9 Density of state of H interacted with different sites of Fe₃O₄ (001)-B

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表 1 H与Fe₃O₄ (001)-B表面作用后的Bader电荷转移分析

Table 1 Bader charge analysis of H interacted with different sites of Fe₃O₄ (001)-B

Fe O_a O_b

△e 0.352 -0.667 -0.695

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