Na助剂调控Fe(111)表面上CO<sub>2</sub>加氢制低碳烯烃反应路径及产物相对选择性的理论研究

田佳荣; 吴华帅; 张效胜; 丁传敏; 王俊文

doi:10.12434/j.issn.2097-2547.20250107

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Na助剂调控Fe(111)表面上CO₂加氢制低碳烯烃反应路径及产物相对选择性的理论研究

C1化学与催化转化 | 更新时间：2026-02-13

- Na助剂调控Fe(111)表面上CO₂加氢制低碳烯烃反应路径及产物相对选择性的理论研究
- Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO₂ hydrogenation to light olefins on Fe(111) surface
- 低碳化学与化工 2026, 51(2): 31-38.
- 作者机构：
  
  太原理工大学化学与化工学院，山西太原 030024
- 作者简介：
  
  田佳荣（1998—），硕士研究生，研究方向为CO2加氢转化制低碳烯烃，E-mail：2979343062@qq.com。
  吴华帅（1988—），博士，讲师，研究方向为CO/CO2加氢高效转化利用，E-mail：wuhuashuai@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金(22308244);山西省基础研究计划(20210302123063)
- DOI：10.12434/j.issn.2097-2547.20250107
  中图分类号： TQ426.94;O643.36
- 收稿：2025-03-17，
  
  修回：2025-04-17，
  
  纸质出版：2026-02-25
- 稿件说明：
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田佳荣,吴华帅,张效胜等.Na助剂调控Fe(111)表面上CO₂加氢制低碳烯烃反应路径及产物相对选择性的理论研究[J].低碳化学与化工,2026,51(2):31-38.

TIAN Jiarong,WU Huashuai,ZHANG Xiaosheng,et al.Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO₂ hydrogenation to light olefins on Fe(111) surface[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(2):31-38.
田佳荣,吴华帅,张效胜等.Na助剂调控Fe(111)表面上CO₂加氢制低碳烯烃反应路径及产物相对选择性的理论研究[J].低碳化学与化工,2026,51(2):31-38. DOI： 10.12434/j.issn.2097-2547.20250107.

TIAN Jiarong,WU Huashuai,ZHANG Xiaosheng,et al.Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO₂ hydrogenation to light olefins on Fe(111) surface[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(2):31-38. DOI： 10.12434/j.issn.2097-2547.20250107.

摘要

Fe基催化剂因具有低廉的成本和优异的催化性能，被广泛应用于CO

加氢制低碳烯烃。加入Na助剂能够明显提高Fe基催化剂的低碳烯烃选择性，但其内在作用机制尚不清晰。采用密度泛函理论（DFT）计算和微观动力学（MKM）分析相结合的方法探究了Na作为助剂对于Fe(111)表面CO

加氢制低碳烯烃反应路径及产物相对选择性的影响。DFT计算表明，添加的Na改变了Fe(111)表面的电子密度，并且明显促进了CO

吸附活化。同时，Na使C

*生成和脱附能垒分别从0.81 eV和1.10 eV降低至0.61 eV和0.46 eV，CH

生成能垒从0.95 eV升高至1.15 eV。MKM分析表明，添加Na明显提高了C

*生成和脱附速率，同时降低了CH

生成速率，整个反应网络体系的速率控制步骤由C

*生成和脱附转变为CH

生成。以上结果从分子水平上揭示了Na通过调控Fe(111)表面的电子结构提高C

生成速率和降低副产物CH

生成速率，进而提高产物C

相对选择性的内在作用机制。

Abstract

Fe-based catalysts

owing to the low cost and excellent catalytic performance

are widely used in

hydrogenation to light olefins. Na can significantly increase the selectivity of light olefins

but the underlying mechanism remains unclear. The influence of Na as a promoter on the reaction pathways and product relative selectivities of CO

hydrogenation to light olefins on the Fe(111) surface was studied by combining density functional theory (DFT) calculations and microkinetic modeling (MKM) analysis. DFT calculations show that Na doping modifies the electron density of the Fe(111) surface and significantly promotes CO

adsorption and activation. Moreover

Na reduces the energy barriers of C

* formation and desorption from 0.81 eV and 1.10 eV to 0.61 eV and 0.46 eV

respectively

and increase the energy barrier of CH

formation from 0.95 eV to 1.15 eV. MKM analysis shows that Na doping substantially increases the rates of C

* formation and desorption and reduces the rate of CH

formation. The rate-determining step of the entire reaction network shifts from C

* formation and desorption to CH

formation. The above results reveal the intrinsic mechanism that Na increases the rates of C

formation and reduces the rates of byproduct CH

formation to increase the C

relative selectivity by regulating electronic structures of the Fe(111) surface at the molecular level.

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references

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Na助剂调控Fe(111)表面上CO2加氢制低碳烯烃反应路径及产物相对选择性的理论研究

Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO2 hydrogenation to light olefins on Fe(111) surface

DOI：10.12434/j.issn.2097-2547.20250107

摘要

Abstract

关键词

Keywords

references

Na助剂调控Fe(111)表面上CO₂加氢制低碳烯烃反应路径及产物相对选择性的理论研究

Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO₂ hydrogenation to light olefins on Fe(111) surface