基于DFT的LaNiO<sub>3</sub>载氧体上化学链蒸汽甲烷重整反应机理研究

周浩哲; 梁志永; 方俊飞

doi:10.12434/j.issn.2097-2547.20250462

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基于DFT的LaNiO₃载氧体上化学链蒸汽甲烷重整反应机理研究

更新时间：2026-03-23

- 基于DFT的LaNiO₃载氧体上化学链蒸汽甲烷重整反应机理研究
- Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO₃ oxygen carrier based on DFT
- 低碳化学与化工 2026: 1-10.
- 作者机构：
  
  1.陕西理工大学机械工程学院，陕西汉中 723000
  2.陕西理工大学陕西省工业自动化重点实验室，陕西汉中 723000
- 作者简介：
  
  周浩哲（2001—），硕士研究生，研究方向为化学链制氢，E-mail：zhouhaozhe@snut.edu.cn。
  梁志永（1985—），博士，讲师，研究方向为化学链制氢，E-mail：junjinxing@163.com。
- 基金信息：
  
  陕西省重点研发计划(2024NC-YBXM-246);陕西省教育厅科学研究计划(21JK0573)
- DOI：10.12434/j.issn.2097-2547.20250462
  中图分类号： TQ038.4
- 收稿：2025-12-02，
  
  修回：2026-01-04，
  
  网络首发：2026-03-19，
- 稿件说明：
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周浩哲,梁志永,方俊飞.基于DFT的LaNiO₃载氧体上化学链蒸汽甲烷重整反应机理研究[J].低碳化学与化工,

ZHOU Haozhe,LIANG Zhiyong,FANG Junfei.Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO₃ oxygen carrier based on DFT[J].Low-Carbon Chemistry and Chemical Engineering,
周浩哲,梁志永,方俊飞.基于DFT的LaNiO₃载氧体上化学链蒸汽甲烷重整反应机理研究[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20250462.

ZHOU Haozhe,LIANG Zhiyong,FANG Junfei.Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO₃ oxygen carrier based on DFT[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20250462.

摘要

化学链蒸汽甲烷重整（CL-SMR）是一种高效转化CH

制备清洁能源的技术，其中，LaNiO

因具有优异的储氧性能和催化活性而被视为潜在的载氧体。然而，CH

在LaNiO

表面的微观转化机理尚未完全明晰，限制了LaNiO

载氧体的定向优化设计。为探究在LaNiO

(110)表面CL-SMR反应机理，基于密度泛函理论（DFT），首先构建了CH

分解过程中各中间体（CH

，

= 0~4）在LaNiO

(110)表面的吸附模型，明确稳定吸附构型。然后，从CH

连续脱氢、CO/CO

生成、H

O生成和氧扩散4个过程解析了微观反应路径。结果表明，CH

在LaNiO

(110)表面的连续脱氢过程中，各中间体与载氧体表面存在较强相互作用，吸附构型稳定，且该过程在热力学有利，反应路径稳定可行。其中，CH脱氢过程所需的能垒因显著高于其他步骤，成为整体反应的速率控制步骤。生成的CO易进一步反应转化为CO

，而H则更倾向于生成H

O。此外，反应消耗表面氧后形成的氧缺陷位可通过体相晶格氧均匀扩散得到补充。LaNiO

载氧体可有效促进CH

转化为CO

和H

O，但需通过降低限速步骤的能垒，进一步提升其催化性能。相关研究结果明确了CH

在LaNiO

(110)表面的反应机理，以期为CL-SMR工艺中高性能LaNiO

载氧体的设计提供理论参考。

Abstract

Chemical looping-steam methane reforming (CL-SMR) enables efficient methane conversion to clean energy

with LaNiO

emerging as a promising oxygen carrier due to its exceptional oxygen storage capacity and catalytic activity. However

the micro mechanism of CH

conversion on LaNiO

surface remains unclear

which limits the directional optimization design of LaNiO

oxygen carrier. To clarify the reaction mechanism of CL-SMR on LaNiO

(110) surface

based on density functional theory (DFT)

adsorption models of various intermediates (CH

= 0~4) on LaNiO

(110) surface during CH

decomposition were first constructed to clarify the stable adsorption configuration. Then the micro reaction path network was analyzed from four core processes: CH

sequential dehydrogenation

CO/CO

formation

O generation and oxygen diffusion. The results show that during the CH

sequential dehydrogenation process on LaNiO

(110) surface

there are strong interactions between the intermediates and the oxygen carrier surface

and the adsorption configurations are stable. The process was thermodynamically favorable and the reaction paths are stable and feasible. Among them

the energy barrier required for the CH dehydrogenation is significantly higher than other steps

identified as the rate-determining step. Generated CO readily oxidizes further to CO

while H prefer forming H

O. What’s more

the oxygen vacancies formed after the consumption of surface oxygen by the reaction can be supplemented by the bulk lattice oxygen diffusion. LaNiO

oxygen carrier can efficiently catalyze CH

conversion to CO

and H

but its catalytic performance needs to be further improved by lowering the energy barrier of rate-determining step. This relevant research results clarify the reaction mechan

ism of CH

on LaNiO

(110) surface

in order to provide a theoretical reference for designing high-performance LaNiO

oxygen carriers for CL-SMR.

关键词

Keywords

references

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基于DFT的LaNiO3载氧体上化学链蒸汽甲烷重整反应机理研究

Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO3 oxygen carrier based on DFT

DOI：10.12434/j.issn.2097-2547.20250462

摘要

Abstract

关键词

Keywords

references

基于DFT的LaNiO₃载氧体上化学链蒸汽甲烷重整反应机理研究

Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO₃ oxygen carrier based on DFT