Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO<sub>3</sub> oxygen carrier based on DFT

ZHOU Haozhe; LIANG Zhiyong; FANG Junfei

doi:10.12434/j.issn.2097-2547.20250462

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

更新时间：2026-05-22

- Study on reaction mechanism of chemical looping-steam methane reforming on LaNiO₃ oxygen carrier based on DFT
- Vol. 51, Issue 5, Pages: 19-28(2026)
- 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：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250462
  CLC： TQ038.4
- Received：02 December 2025，
  
  Revised：2026-01-04，
  
  Published：25 May 2026
- 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,2026,51(5):19-28.

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,2026,51(5):19-28.
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,2026,51(5):19-28. 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,2026,51(5):19-28. 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，明确了稳定吸附构型。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，且该过程在热力学上有利，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 e

nergy

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 is 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 mechanism of CH

on LaNiO

(110) surface

in order to provide a theoretical reference fo

r designing high-performance LaNiO

oxygen carriers for CL-SMR.

关键词

Keywords

references

LIU T , YU Z L , LI G , et al . Performance of potassium-modified Fe 2 O 3 /Al 2 O 3 oxygen carrier in coal-direct chemical looping hydrogen generation [J ] . International Journal of Hydrogen Energy , 2018 , 43 ( 42 ): 19384 - 19395 .

张涛 , 宋涛 . 化学链燃烧技术研究进展 [J ] . 电力科技与环保 , 2024 , 40 ( 6 ): 582 - 590 .

ZHANG T , SONG T . Research progress of chemical looping combustion [J ] . Electric Power Technology and Environmental Protection , 2024 , 40 ( 6 ): 582 - 590 .

郑浩 , 孙朝 , 曾亮 . 化学链技术在低碳制氢领域的研究进展 [J ] . 中南大学学报（自然科学版） , 2021 , 52 ( 1 ): 313 - 329 .

ZHENG H , SUN Z , ZENG L . Research progress of chemical looping technology for low-carbon hydrogen generation [J ] . Journal of Central South University (Science and Technology) , 2021 , 52 ( 1 ): 313 - 329 .

CHENG Z , QIN L , FAN J A , et al . New insight into the development of oxygen carrier materials for chemical looping systems [J ] . Engineering , 2018 , 4 ( 3 ): 343 - 351 .

OSMAN M , KHAN M N , ZAABOUT A , et al . Review of pressurized chemical looping pro cesses for power generation and chemical production with integrated CO 2 capture [J ] . Fuel Processing Technology , 2021 , 214 : 106684 .

ZENG D W , LI Y Z , ZHANG Z W , et al . Bulk oxygen conduction kinetics of iron oxides on the chemical looping combustion [J ] . Fuel Processing Technology , 2022 , 237 : 107442 .

ABUELGASIM S , WANG W J , ABDALAZEEZ A . A brief review for chemical looping combustion as a promising CO 2 capture technology: Fundamentals and progress [J ] . Science of the Total Environment , 2021 , 764 : 142892 .

MOLDENHAUER P , LINDERHOLM C , RYDEN M , et al . Avoiding CO 2 capture effort and cost for negative CO 2 emissions using industrial waste in chemical-looping combustion/gasification of biomass [J ] . Mitigation and Adaptation Strategies for Global Change , 2020 , 25 ( 1 ): 1 - 24 .

DI G A , CAPONE S , ANATONE M , et al . Chemical looping combustion and gasification: A review and a focus on european research projects [J ] . Industrial & Engineering Chemistry Research , 2022 , 61 ( 39 ): 14403 - 14432 .

任金丽 , 张根宁 , 沈秋婉 , 等 . 基于化学链甲烷重整制氢的钙钛矿载氧体研究综述 [J ] . 燃料化学学报（中英文） , 2025 , 53 ( 4 ): 419 - 433 .

REN J L , ZHANG G N , SHEN Q W , et al . A review of research on perovskite oxygen carrier for chemicallooping reforming of methane [J ] . Journal of Fuel Chemistry and Technology , 2025 , 53 ( 4 ): 419 - 433 .

LI G , CHANG Y X , LIU T , et al . Hydrogen element flow and economic analyses of a coal direct chemical looping hydrogen generation process [J ] . Energy , 2020 , 206 : 118243 .

LEWIS W K , GILLILAND E R . Production of pure carbon dioxide : US2665972A [P ] . 1954-01-12 .

ISHIDA M , JIN H A . New advanced power-generation system using chemical-looping combustion [J ] . Energy , 1994 , 19 ( 4 ): 415 - 422 .

ISHIDA M , JIN H A . Novel combustor based on chemical-looping reactions and its reaction kinetics [J ] . Journal of Chemical Engineering of Japan , 1994 , 27 ( 3 ): 296 - 301 .

WANG Y J , ZHENG Y N , WANG Y H , et al . Evaluation of Fe substitution in perovskite LaMnO 3 for the production of high purity syngas and hydrogen [J ] . Journal of Power Sources , 2020 , 449 : 227505 .

NAZARI M , SOLTANIEH M , HEYDARINASAB A , et al . Synthesis of a new self-supported Mg y (Cu x Ni 0.6- x Mn 0.4 ) 1- y Fe 2 O 4 oxygen carrier f or chemical looping steam methane reforming process [J ] . International Journal of Hydrogen Energy , 2021 , 46 ( 37 ): 19397 - 19420 .

倪永明 , 邓冀童 , 乔韦军 , 等 . 甲烷化学链燃烧技术中氧载体的研究进展 [J ] . 低碳化学与化工 , 2023 , 48 ( 4 ): 8 - 15 .

NI Y M , DENG J T , QIAO W J , et al . Research progress on oxygen carrier in chemical-looping combustion of methane [J ] . Low-Carbon Chemistry and Chemical Engineering , 2023 , 48 ( 4 ): 8 - 15 .

MINAZAM E R , BREAULT R W , SIRIWARDANE R . Reduction of hematite (Fe 2 O 3 ) to wustite (FeO) by carbon monoxide (CO) for chemical looping combustion [J ] . Chemical Engineering Journal , 2014 , 242 : 204 - 210 .

SAHA C , ROY B , BHTTACHARYA S . Chemical looping combustion of victorian brown coal using NiO oxygen carrier [J ] . International Journal of Hydrogen Energy , 2011 , 36 ( 4 ): 3253 - 3259 .

HWANG J H , BAEK J I , RYU H J , et al . Development of MgMnO 3- δ as an oxygen carrier material for chemical looping combustion [J ] . Fuel , 2018 , 231 : 290 - 296 .

CHANG W X , HU Y , XU W B , et al . Recent advances of oxygen carriers for hydrogen production via chemical looping water-splitting [J ] . Catalysts , 2023 , 13 ( 2 ): 279 .

张善超 , 张德亮 , 王露 , 等 . 铁基钙钛矿载氧体化学链制合成气热力学性能分析与实验 [J ] . 化工进展 , 2025 , 44 ( 10 ): 5703 - 5716 .

ZHANG S C , ZHANG D L , WANG L , et al . Thermodynamic analysis and experimental study on the iron-based perovskite oxygen carrier for syngas production via chemical looping [J ] . Chemical Industry and Engineering Progress , 2025 , 44 ( 10 ): 5703 - 5716 .

杨柳青 , 赵子瑞 , 张军社 , 等 . 钡含量对(La 0.5 Sr 0.5 ) 1 - x Ba x Fe 0.6 Co 0.4 O 3 化学链甲烷干重整性能的影响 [J ] . 化工学报 , 2023 , 74 ( 10 ): 4286 - 4301 .

YANG L Q , ZHAO Z R , ZHANG J S , et al . Effect of Ba content on chemical looping dry reforming of methane performance of (La 0.5 Sr 0.5 ) 1- x Ba x Fe 0.6 Co 0.4 O 3 [J ] . CIESC Journal , 2023 , 74 ( 10 ): 4286 - 4301 .

高孟良 . 改性镧铁双钙钛矿载氧体在化学链甲烷蒸汽重整中的性能研究 [D ] . 重庆 : 重庆大学 , 2024 .

GAO M L . Performance of modified lanthanum-Iron double perovskite oxygen carriers in chemical looping steam methane reforming [D ] . Chongqing : Chongqing University , 2024 .

杨杰 , 常辉 , 隋志军 , 等 . 化学链催化甲烷氧化反应研究进展 [J ] . 化工进展 , 2021 , 40 ( 4 ): 1928 - 1947 .

YANG J , CHANG H , SUI Z J , et al . Advances in chemical looping methane oxidation [J ] . Advances in Chemical Looping Methane Oxidation , 2021 , 40 ( 4 ): 1928 - 1947 .

王智超 , 梁威 , 刘根 , 等 . Mn 2 O 3 @SiO 2 载氧体用于乙烷化学链氧化脱氢制乙烯性能研究 [J ] . 低碳化学与化工 , 2025 , 50 ( 8 ): 133 - 143 .

WANG Z C , LIANG W , LIU G , et al . Performance study of Mn 2 O 3 @SiO 2 oxygen carrier for chemical looping oxidative dehydrogenation of ethane to ethylene [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 8 ): 133 - 143 .

SHEN Y , ZHAO K , HE F , et al . The structure-reactivity relationships of using three-dimensionally ordered macroporous LaFe 1- x Ni x O 3 perovskites for chemical-looping steam methane reforming [J ] . Journal of the Energy Institute , 2019 , 92 ( 2 ): 239 - 246 .

EVDOU A , ZASPALIS V . Comparative evaluation of various ABO 3 perovskites (A = La, Ca, Sr; B = Mn, Fe) as oxygen carrier materials in chemical looping hydrogen production [J ] . Hydrogen , 2025 , 6 ( 2 ): 27 .

YIN X , SHEN L , WANG S , et al . Double adjustment of Co and Sr in LaMnO 3+ δ perovskite oxygen carriers for chemical looping steam methane reforming [J ] . Applied Catalysis B: Environment and Energy , 2022 , 2 : 120816 .

FÜNGERLINGS A , WOHLGEMUTH M , ANTIPIN D , et al . Crystal-facet-dependent surface transformation dictates the oxygen evolution reaction activity in lanthanum nickelate [J ] . Nature Communications , 2023 , 14 ( 1 ): 8284 .

AU C T , NG C F , LIAO M S . Methane dissociation and syngas formation on Ru, Os, Rh, Ir, Pd, Pt, Cu, Ag, and Au: A theoretical study [J ] . Journal of Catalysis , 1999 , 185 ( 1 ): 12 - 22 .

PAN C C , CHEN Y H , WU N , et al . A first principles study of H 2 adsorption on LaNiO 3 (001) surfaces [J ] . Materials , 2017 , 10 ( 1 ): 36 .

LIU C L , LI S , DONG C , et al . Hydrogen-rich syngas production by chemical looping steam reforming of acetic acid as bio-oil model compound over Fe-doped LaNiO 3 oxygen carriers [J ] . International Journal of Hydrogen Energy , 2019 , 44 ( 33 ): 17732 - 17741 .

YAO X , ZHANG X H , LIU R , et al . Oxygen activity regulation over LaNiO 3 perovskites by Ti substitution for chemical looping partial oxidation of methane [J ] . Chemical Engineering Science , 2023 , 278 : 118911 .

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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

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