Theoretical calculation study on effects of H coverage on CO activation in Fischer-Tropsch synthesis catalysts

WANG Yuxin; LIU Bing; LIU Xiaohao

doi:10.12434/j.issn.2097-2547.20240049

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Theoretical calculation study on effects of H coverage on CO activation in Fischer-Tropsch synthesis catalysts

- Theoretical calculation study on effects of H coverage on CO activation in Fischer-Tropsch synthesis catalysts
- Vol. 49, Issue 8, Pages: 10-17(2024)
- 作者机构：
  
  江南大学化学与材料工程学院，江苏无锡 214122
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240049
  CLC： TQ426
- Published：25 August 2024，
  
  Received：05 February 2024，
  
  Revised：04 March 2024，
- 稿件说明：
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王雨欣,刘冰,刘小浩.H覆盖对费托合成催化剂CO活化影响的理论计算研究[J].低碳化学与化工,2024,49(08):10-17.

WANG Yuxin,LIU Bing,LIU Xiaohao.Theoretical calculation study on effects of H coverage on CO activation in Fischer-Tropsch synthesis catalysts[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):10-17.
王雨欣,刘冰,刘小浩.H覆盖对费托合成催化剂CO活化影响的理论计算研究[J].低碳化学与化工,2024,49(08):10-17. DOI： 10.12434/j.issn.2097-2547.20240049.

WANG Yuxin,LIU Bing,LIU Xiaohao.Theoretical calculation study on effects of H coverage on CO activation in Fischer-Tropsch synthesis catalysts[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):10-17. DOI： 10.12434/j.issn.2097-2547.20240049.

摘要

Fe基和Co基催化剂是最理想的费托合成催化剂，随着计算机模拟技术在催化领域快速地发展，深入理解Fe基和Co基催化剂表面的微观反应机理成为可能。采用理论计算方法，研究了不同H覆盖度的Fe基（反应条件：温度320 ℃、压力1 MPa以及

(CO) = 1:1）、Co基（反应条件：温度240 ℃、压力1 MPa以及

(CO) = 2:1）费托合成催化剂的表面结构以及H覆盖对CO活化与解离的影响。通过氢气化学势与氢吸附吉布斯自由能的线性关系确定了Fe基、Co基费托合成催化剂热力学最优的H覆盖表面模型，分别为H覆盖度为11/42的

-Fe

(510)表面和H覆盖度为24/36的HCP Co(0001)表面。研究了洁净的催化剂表面与H覆盖的催化剂表面的CO解离机理及相关反应能垒，发现H覆盖会改变CO解离路径且增大CO解离能垒，相较于洁净的

-Fe

(510)和HCP Co(0001)表面，H覆盖的

-Fe

(510)和HCP Co(0001)表面的CO解离能垒分别升高了5.4%和20.3%。通过对表面态密度以及晶体轨道哈密顿布居的计算解释了H覆盖影响CO活化与解离的本质原因。

Abstract

Fe-based and Co-based catalysts are the most ideal Fischer-Tropsch synthesis catalysts. With the rapid development of computer simulation technology in the field of catalysis

it is possible to deeply understand the microscopic reaction mechanism on the surface of Fe-based and Co-based catalysts. Theoretical calculation method was used to study the effects of surface structures of Fe-based (reaction conditions: temperature 320 ℃

pressure 1 MPa and

(CO) = 1:1) and Co-based (reaction conditions: temperature 240 ℃

pressure 1 MPa and

(CO) = 2:1) Fischer-Tropsch synthesis catalysts with different H coverages on the activation and dissociation of CO. The thermodynamically preferred H-covered surface models

of Fe-based and Co-based Fischer-Tropsch synthesis catalysts were determined through the linear relationships between the hydrogen chemical potential and the Gibbs free energy of hydrogen adsorption

which is the

-Fe

(510) surface with H coverage of 11/42 and HCP Co(0001) surface with H coverage of 24/36

respectively. The CO dissociation mechanism and corresponding reaction energy barriers on the clean surface and the H-covered surface of catalysts were studied

and it is found that H coverage can change the reaction pathways of CO dissociation and increase the dissociation energy barrier. Compared with the clean surfaces of

-Fe

(510) and HCP Co(0001)

the dissociation energy barriers of CO on H-covered

-Fe

(510) and HCP Co(0001) surfaces increase by 5.4% and 20.3%

respectively. The origin reasons for the effects of H coverage on CO activation and dissociation were explained by calculating the density of states and crystal orbitals Hamiltonian population.

关键词

费托合成催化剂CO活化H覆盖DFT计算

Keywords

Fischer-Tropsch synthesis catalystsCO activationH coverageDFT calculation

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