Reactivity of low-concentration Cu-doped modified Fe-based oxygen carrier in chemical looping: experiments and theoretical simulations

YUAN Nini; BAI Hongcun; AN Mei; HU Xiude; GUO Qingjie

doi:10.11949/0438-1157.20200307

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Reactivity of low-concentration Cu-doped modified Fe-based oxygen carrier in chemical looping: experiments and theoretical simulations

Energy and environmental engineering | 更新时间：2026-07-24

- Reactivity of low-concentration Cu-doped modified Fe-based oxygen carrier in chemical looping: experiments and theoretical simulations
- CIESC Journal Vol. 71, Issue 11, Pages: 5294-5302(2020)
- 作者机构：
  
  宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室，化学化工学院，宁夏银川 750021
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200307
  CLC： TQ 530.11
- Received：23 March 2020，
  
  Revised：2020-06-01，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
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袁妮妮, 白红存, 安梅, 胡修德, 郭庆杰. 化学链过程中Cu低浓度掺杂改性Fe-基载氧体反应性能:实验与理论模拟[J]. 化工学报, 2020, 71(11): 5294-5302

YUAN Nini, BAI Hongcun, AN Mei, HU Xiude, GUO Qingjie. Reactivity of low-concentration Cu-doped modified Fe-based oxygen carrier in chemical looping: experiments and theoretical simulations[J]. CIESC Journal, 2020, 71(11): 5294-5302
袁妮妮, 白红存, 安梅, 胡修德, 郭庆杰. 化学链过程中Cu低浓度掺杂改性Fe-基载氧体反应性能:实验与理论模拟[J]. 化工学报, 2020, 71(11): 5294-5302 DOI： 10.11949/0438-1157.20200307.

YUAN Nini, BAI Hongcun, AN Mei, HU Xiude, GUO Qingjie. Reactivity of low-concentration Cu-doped modified Fe-based oxygen carrier in chemical looping: experiments and theoretical simulations[J]. CIESC Journal, 2020, 71(11): 5294-5302 DOI： 10.11949/0438-1157.20200307.

摘要

基于热重实验（TGA）和密度泛函理论（DFT）计算，对Cu低浓度掺杂Fe

载氧体（Cu-Fe

）与H

在化学链燃烧过程中反应活性和微观分子反应机理进行研究。TGA结果显示，Cu低浓度掺杂降低Fe

载氧体与H

反应表观活化能

（从83.9 kJ/mol降低至72.3 kJ/mol），因此，低浓度Cu掺杂由于原子尺度Cu掺杂缺陷的引入的确提高了Fe

载氧体转化率和晶格氧释放速率。DFT计算从分子水平证实Cu低浓度掺杂改变了Fe

载氧体与H

反应路径，路径分析表明，Cu掺杂使Fe

载氧体与H

反应能垒从2.30 eV分别降低至1.81 eV（Fe原子top位反应）和1.68 eV（Cu原子top位反应），Cu掺杂的Fe-基载氧体的氢还原反应优先发生在掺杂的Cu原子位，其次为Fe原子位。此外，计算结果表明，因Cu-O和Cu-Fe键的引入，低浓度Cu掺杂改变了Fe

载氧体微观结构，这对于载氧体的晶格氧快速释放是有利的。

Abstract

Based on thermogravimetric experiment (TGA) and density functional theory (DFT) calculations

the reaction activity and microscopic molecular reaction mechanism of Cu low-concentration doped Fe

oxygen carrier (Cu-Fe

) and H

in the process of chemical looping combustion were studied. TGA results showed that the low concentration of Cu-doped reduced the apparent activation energy of Fe

reaction with H

(from 83.9 kJ/mol to 72.3 kJ/mol). And improved the conversion rate and lattice oxygen release rate of Fe

oxygen carrier

which was attributed to the introduction of Cu element. From the atom/molecular level

DFT calculations verified that the low concentration of Cu-doped altered reaction pathway of Fe

oxygen carrier reaction with H

. The calculation results showed that the energy barrier of Fe

oxygen carrier reaction with H

decreased from 2.30 eV to 1.81 eV (Fe atom top site) and 1.68 eV (Cu atom top site)

respectively. The reaction preferentially occurred at the Cu atom site

followed at Fe atom site. Furthermore

the micro-structure characteristic change of Fe

oxygen carrier (Cu—O and Cu—Fe bonds introduced) is more favorable for the rapid lattice oxygen release in chemical looping process.

关键词

Keywords

references

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