Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO<sub>2</sub> hydrogenation to light olefins on Fe(111) surface

TIAN Jiarong; WU Huashuai; ZHANG Xiaosheng; DING Chuanmin; WANG Junwen

doi:10.12434/j.issn.2097-2547.20250107

您当前的位置：

首页 >

文章列表页 >

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

更新时间：2026-02-13

- Theoretical study on Na promoter-regulated reaction pathways and product relative selectivity of CO₂ hydrogenation to light olefins on Fe(111) surface
- Vol. 51, Issue 2, Pages: 31-38(2026)
- 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：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250107
  CLC： TQ426.94;O643.36
- Received：17 March 2025，
  
  Revised：2025-04-17，
  
  Published：25 February 2026
- 稿件说明：
移动端阅览
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.

关键词

Keywords

references

丁祎 . 制低碳烯烃过程中二氧化碳吸附的密度泛函研究 [D ] . 北京 : 中国石油大学（北京） , 2022 .

DING Y . Density functional theory study on CO 2 adsorption in the process of preparing low carbon alkenes [D ] . Beijing : China University of Petroleum (Beijing) , 2022 .

DORNER R W , HARDY D R , WILLIAMS F W , et al . Influence of gas feed composition and pressure on the catalytic conversion of CO 2 to hydrocarbons using a traditional cobalt-based Fischer-Tropsch catalyst [J ] . Energy Fuels , 2009 , 23 ( 8 ): 4190 - 4195 .

WANG W , WANG S P , MA X B , et al . Recent advances in catalytic hydrogenation of carbon dioxide [J ] . Chemical Society Reviews , 2011 , 40 ( 7 ): 3703 - 3727 .

SHAFER W D , JACOBS G , GRAHAM U M , et al . Increased CO 2 hydrogenation to liquid products using promoted iron catalysts [J ] . Journal of Catalysis , 2019 , 369 : 239 - 248 .

AMOYAL M , VIDRUK-NEHEMYA R , LANDAU M V , et al . Effect of potassium on the active phases of Fe catalysts for carbon dioxide conversion to liquid fuels through hydrogenation [J ] . Journal of Catalysis , 2017 , 348 : 29 - 39 .

NING W S , KOIZUMI N , YAMADA M . Researching Fe catalyst suitable for CO 2 -containing syngas for Fischer-Tropsch synthesis [J ] . Energy & Fuels , 2009 , 23 ( 9 ): 4696 - 4700 .

LIANG B L , SUN T , MA J G , et al . Mn decorated Na/Fe catalysts for CO 2 hydrogenation to light olefins [J ] . Catalysis Science & Technology , 2019 , 9 ( 2 ): 456 - 464 .

DORNER R W , HARDY D R , WILLIAMS F W , et al . K and Mn doped iron-based CO 2 hydrogenation catalysts: Detection of KAlH 4 as part of the catalyst’s active phase [J ] . Applied Catalysis A: General , 2010 , 373 ( 1 ): 112 - 121 .

DRY M E , SHINGLES T , BOSHOFF L J , et al . Heats of chemisorption on promoted iron surfaces and the role of alkali in Fischer-Tropsch synthesis [J ] . Journal of Catalysis , 1969 , 15 ( 2 ): 190 - 199 .

XU Y , ZHAI P , DENG Y C , et al . Highly selective olefin production from CO 2 hydrogenation on iron catalysts: A subtle synergy betwee n manganese and sodium additives [J ] . Angewandte Chemie International Edition , 2020 , 59 ( 48 ), 21736 - 21744 .

LIU X L , ZHANG C , TIAN P F , et al . Revealing the effect of sodium on iron-based catalysts for CO 2 hydrogenation: Insights from calculation and experiment [J ] . Journal of Physical Chemistry C , 2021 , 125 ( 14 ): 7904 - 7913 .

LIU J H , ZHANG A F , LIU M , et al . Fe-MOF-derived highly active catalysts for carbon dioxide hydrogenation to valuable hydrocarbons [J ] . Journal of CO 2 Utilization , 2017 , 21 : 100 - 107 .

YAO R W , WEI J , GE Q J , et al . Structure sensitivity of iron oxide catalyst for CO 2 hydrogenation [J ] . Catalysis Today , 2021 , 371 : 134 - 141 .

RAVEL B , NEWVILLE M. ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT [J ] . Journal of Synchrotron Radiat , 2005 , 12 : 537 - 541 .

ZHAI P , XU C , GAO R , et al . Highly tunable selectivity for syngas-derived alkenes over zinc and sodium-modulated Fe 5 C 2 catalyst [J ] . Angewandte Chemie International Edition , 2016 , 55 ( 34 ): 9902 - 9907 .

KRESSE G , FURTHMÜLLER J . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J ] . Physical Review B , 1996 , 54 ( 16 ): 11169 - 11186 .

KRESSE G , HAFNER J . Ab initio molecular-dynamics simulation of the electronic structure of solids [J ] . Physical Review B , 1993 , 47 ( 1 ): 558 - 561 .

PERDEW J P , BURKE K , ERNZERHOF M . Generalized gradient approximation made simple [J ] . Physical Review Letters , 1996 , 77 : 3865 - 3868 .

KRESSE G , JOUBERT D . From ultrasoft pseudopotentials to the projector augmented-wave method [J ] . Physical Review B , 1999 , 59 ( 3 ): 1758 - 1775 .

HENKELMAN G , ARNALDSSON A , JÓNSSON H . A fast and robust algorithm for bader decomposition of charge density [J ] . Computational Materials Science , 2006 , 36 ( 3 ): 354 - 360 .

LIU S L , LI Y W , WANG J G , et al . Reaction of CO, H 2 O, H 2 and CO 2 on the clean as well as O, OH and H precovered Fe(100) and Fe(111) surfaces [J ] . Catalysis Science & Technology , 2017 , 7 ( 2 ): 427 - 440 .

LIU B , LI W P , ZHENG J , et al . CO 2 formation mechanism in Fischer-Tr opsch synthesis over iron-based catalysts: A combined experimental and theoretical study [J ] . Catalysis Science & Technology , 2014 , 118 ( 36 ): 20472 - 20480 .

KITTEL C . Introduction to solid state physics [M ] . 8th ed . New York : Wiley , 1996 .

WANG H Z , NIE X W , LIU Y , et al . Mechanistic insight into hydrocarbon synthesis via CO 2 hydrogenation on χ -Fe 5 C 2 catalysts [J ] . ACS Applied Materials & Interfaces , 2022 , 14 ( 15 ): 17822 - 17831 .

STEGELMANN C , ANDREASEN A , CAMPBELL C T . Degree of rate control: How much the energies of intermediates and transition states control rates [J ] . Journal of the American Chemical Society , 2009 , 131 ( 23 ): 8077 - 8082 .

LIANG B L , DUAN H M , SUN T , et al . Effect of Na promoter on Fe-based catalyst for CO 2 hydrogenation to alkenes [J ] . ACS Sustainable Chemistry & Engineering , 2019 , 7 ( 1 ): 925 - 932 .

YAN B H , ZHAO B H , KATTEL S , et al . Tuning CO 2 hydrogenation selectivity via metal-oxide interfacial sites [J ] . Journal of Catalysis , 2019 , 374 : 60 - 71 .

STERK E B . CO 2 Methanation over Ni and its structure sensitivity: A computational study [D ] . Utrecht : Utrecht University , 2018 .

NIE X W , WANG H Z , JANIK M J , et al . Mechanistic insight into C—C coupling over Fe-Cu bimetallic catalysts in CO 2 hydrogenation [J ] . The Journal of Physical Chemistry C , 2017 , 121 ( 24 ): 13164 - 13174 .

PSARRAS P C , WILCOX J , BALL D W . Effect of Ag and Pd promotion on CH 4 selectivity in Fe(100) Fischer-Tröpsch catalysis [J ] . Physical Chemistry Chemical Physics , 2017 , 19 ( 7 ): 5495 - 5503 .

NIE X W , MENG L L , WANG H Z , et al . DFT insight into the effect of potassium on the adsorption, activatio n and dissociation of CO 2 over Fe-based catalysts [J ] . Physical Chemistry Chemical Physics , 2018 , 20 ( 21 ): 14694 - 14707 .

CHEN J F , JIA M L , HU P J , et al . CATKINAS: A large-scale catalytic microkinetic analysis software for mechanism auto-analysis and catalyst screening [J ] . Journal of Computational Chemistry , 2021 , 42 ( 5 ): 431 - 440 .

ZHU J , WANG P , ZHANG X B , et al . Dynamic structural evolution of iron catalysts involving competitive oxidation and carburization during CO 2 hydrogenation [J ] . Science Advances , 2022 , 8 ( 5 ): 3629 .

DRY M E . The Fischer-Tropsch process: 1950—2000 [J ] . Catalysis Today , 2002 , 71 ( 3 ): 227 - 241 .

MOTAGAMWALA A H , DUMESIC J A . Microkinetic modeling: A tool for rational catalyst design [J ] . Chemical Reviews , 2020 , 121 ( 2 ): 1309 - 1337 .

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Research progress on catalysts for thermal catalytic CO₂ hydrogenation to olefins

Effects of supports on catalytic performances of Fe-based catalysts for CO₂ hydrogenation to light olefins

Research progress on active phases regulation of iron-based catalysts and their CO₂ catalytic hydrogenation to linear α-olefins

Vibration Influence on the Existed Railway Tunnel by Blasting Construction of Underpass Diversion Tunnel and Countermeasures

Experimental Study of the Bond Strength at the Interface of Reactive Powder Concrete-Filled Steel Tube Columns

Related Author

TIAN Jiarong

WU Huashuai

LI Huayong

XING Xiaofang

LIN Shiyuan

WANG Yang

WU Mingbo

LI Guanghui

Related Institution

College of New Energy, College of Chemistry and Chemical Engineering, China University of Petroleum (East China)

Beiouyi (Shandong) New Material Co., Ltd.

State Key Laboratory of Coking Coal Resources Green Exploitation, Zhengzhou University

Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education, School of Chemical Engineering, Zhengzhou University

State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University

Postal code：610225
Tel：028-85964717 Email：236764603@qq.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：378882 Visits Today：30

⁰

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

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