基于镍-锆酸钠吸附-催化双功能材料的甲烷重整机理研究

孙超; 谢华清; 徐海健; 张树; 刘坤

doi:10.19944/j.eptep.1674-8069.2025.03.003

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基于镍-锆酸钠吸附-催化双功能材料的甲烷重整机理研究

双碳背景下电力行业绿色催化技术 | 更新时间：2026-10-14

- 基于镍-锆酸钠吸附-催化双功能材料的甲烷重整机理研究
- Research on the mechanism of methane reforming based on Ni-Na₂ZrO₃ adsorption-catalytic bifunctional material
- 电力科技与环保 2025年41卷第3期页码：373-382
- 作者机构：
  
  1.东北大学冶金学院，辽宁沈阳 110819
  2.山东一然环保科技有限公司，山东济南 250200
- 作者简介：
  
  孙超（2001—），男，硕士研究生，主要从事双功能材料，二氧化碳捕集利用等方面的研究，13100120669@163.com
  谢华清（1987—），男，副教授，主要从事低碳能源开发与二氧化碳捕集利用，制氢技术，生物质高效转化与利用，余热余能回收利用等方面的研究，xiehq@mail.neu.edu.cn；
  徐海健（1980—），女，工程师，主要从事炉窑热工，高效燃烧与环保等方面的研究，1628442822@qq.com；
  张树（2000—），男，硕士研究生，主要从事焦油催化裂解，二氧化碳利用等方面的研究，zs000308@163.com；
  刘坤（2001—），男，硕士研究生，主要从事流体仿真和颗粒耦合模拟等方面研究，715156757@qq.com。
- 基金信息：
  
  国家自然科学基金项目(52476181)
- DOI：10.19944/j.eptep.1674-8069.2025.03.003
  中图分类号： TK02;TQ152
- 收稿：2024-12-12，
  
  录用：2025-05-10，
  
  纸质出版：2025-06-15
- 稿件说明：
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孙超,谢华清,徐海健，等.基于镍-锆酸钠吸附-催化双功能材料的甲烷重整机理研究[J].电力科技与环保,2025,41(3):373-382.

SUN Chao, XIE Huaqing, XU Haijian, et al. Research on the mechanism of methane reforming based on Ni-Na₂ZrO₃ adsorption-catalytic bifunctional material[J]. Electric Power Technology and Environmental Protection, 2025, 41(3):373-382. DOI: 10.19944/j.eptep.1674-8069.2025.03.003.
孙超,谢华清,徐海健，等.基于镍-锆酸钠吸附-催化双功能材料的甲烷重整机理研究[J].电力科技与环保,2025,41(3):373-382. DOI： 10.19944/j.eptep.1674-8069.2025.03.003.

SUN Chao, XIE Huaqing, XU Haijian, et al. Research on the mechanism of methane reforming based on Ni-Na₂ZrO₃ adsorption-catalytic bifunctional material[J]. Electric Power Technology and Environmental Protection, 2025, 41(3):373-382. DOI: 10.19944/j.eptep.1674-8069.2025.03.003. DOI：

摘要

目的

为揭示镍-锆酸钠（Ni-Na₂ZrO₃）吸附-催化双功能材料在吸附增强甲烷（CH

）蒸汽重整中的微观反应机理，以解决传统CH

重整技术中CO₂分离能耗高、催化剂积碳严重等问题。通过理论模拟优化材料设计，为开发高效、低能耗的双功能材料提供科学依据，推动氢能规模化应用及碳中和目标的实现。

方法

基于密度泛函理论，构建Ni-Na₂ZrO₃表面模型，系统分析21种吸附质，包括CH

、CH

OH、CO、CO₂等在不同吸附位点的吸附能及竞争吸附特性。通过过渡态计算确定34个基元反应的能垒，探究CH

解离、中间产物转化及CO₂生成的动力学路径。结合表面能、吸附能及反应能垒数据，揭示碳转化路径的关键步骤与限速环节。进一步对比Na₂ZrO₃与Ni-Na₂ZrO₃的CO₂吸附-解吸性能，评估Ni掺杂对材料再生能力的影响。

结果

研究表明，CH

和CH

OH的吸附能随脱氢程度加深而显著增强，C吸附能为-8.69 eV，而CH₄仅为-0.45 eV，表明脱氢产物与表面相互作用增强。最终产物中，H₂吸附能较低，为-0.42 eV，易于逸散，而CO₂吸附稳定，为-0.55 eV，实现原位分离。CH

解离最优路

径为直接脱氢路径（CH₄→CH₃→CH₂→CH），其中CH₃→CH₂+H为限速步骤，能垒为1.59 eV。Ni掺杂显著提升材料再生性能：Ni-Na₂CO₃对ZrO₂的吸附能由原有-4.90 eV增至-9.74 eV，且CO₂解吸能垒从4.90 eV降至2.05 eV，大幅降低再生能耗。

结论

Ni-Na₂ZrO₃双功能材料在吸附增加CH

水蒸气重整制氢中展现出高效碳转化能力与优异的循环稳定性。其最优反应路径通过直接脱氢与CHOH路径耦合实现，限速步骤明确；Ni的引入通过强化吸附界面与降低解吸能垒，显著提升CO₂捕集与材料再生效率。本研究为设计兼具高催化活性与再生能力的双功能材料提供了理论框架，对推动低能耗制氢与碳捕集技术发展具有重要指导意义。

Abstract

Objective

This study aims to elucidate the microscopic reaction mechanism of Ni-Na

ZrO

bifunctional material in sorption-enhanced methane steam reforming

addressing the challenges of high energy consumption in CO

separation and severe carbon deposition in traditional methane reforming. By optimizing material design through theoretical simulations

it provides a scientific basis for developing efficient and low-energy bifunctional materials

promoting the large-scale application of hydrogen energy and achieving carbon neutrality goals.

Methods

Based on density functional theory

a Ni-Na

ZrO

surface model was constructed to systematically analyze the adsorption energies and competitive adsorption characteristics of 21 adsorbates (including CHₓ

CHₓOH

etc.) at different adsorption sites. Transition state calculations were performed to determine the energy barriers of 34 elementary reactions

investigating the kinetic pathways of methane dissociation

intermediate conversion

and CO

formation. Key steps and rate-limiting stages of carbon conversion were identified by integrating surface energy

adsorption energy

and reaction barrier data. Furthermore

the CO

adsorption-desorption performance of Na

ZrO

and Ni-Na

ZrO

was compared to evaluate the impact of Ni doping on material regenerability.

Results

The results indicate that the absolute adsorption en

ergy of CH

ₓ

and CH

ₓ

OH increases significantly with dehydrogenation

C adsorption energy: -8.69 eV vs. CH₄: -0.45 eV

demonstrating enhanced interaction between dehydrogenated species and the surface. Among the products

exhibits weak adsorption

facilitating its desorption

while CO₂ remains stably adsorbed

enabling in-situ separation. The optimal methane dissociation pathway follows direct dehydrogenation (CH

→CH₃→CH₂→CH)

with CH₃→CH₂+H as the rate-limiting step (energy barrier: 1.59 eV). The intermediate CH generates CO via the CHOH pathway (barrier: 1.38 eV)

and CO is further oxidized to CO₂ with O atoms provided by OH dissociation . Ni doping significantly enhances regenerability: the adsorption energy of ZrO₂ on Ni-Na₂CO₃ increases to -9.74 eV

and the CO₂ desorption barrier decreases from 4.90 eV to 2.05 eV

drastically reducing regeneration energy consumption.

Conclusion

The Ni-Na

ZrO

bifunctional material demonstrates high carbon conversion efficiency and exceptional cyclic stability in SESMR. The optimal reaction pathway (CH₄→CO₂) is achieved through coupling direct dehydrogenation and the CHOH pathway

with clearly defined rate-limiting steps. Ni incorporation strengthens the adsorption interface and lowers desorption barriers

significantly improving CO₂ capture and material regeneration. This study establishes a theoretical framework for designing dual-function materials with high catalytic activity and regenerability

offering critical insights for advancing low-energy hydrogen production and carbon capture technologies.

关键词

Keywords

references

佟伟 . 未来燃料赋能“氢经济”——霍尼韦尔发布《未来燃料——霍尼韦尔氢能工业与应用白皮书》 [J ] . 现代制造， 2022 ，( 12 ): 18 - 19 .

TONG Wei . Fuel of the future-A white paper of honeywell technologies for hydrogen industry and applications [J ] . Maschinen Markt ， 2022 ，( 12 ): 18 - 19 .

焦健，陈彬剑，刁文鹏，等 . 甲烷水蒸气重整制氢技术研究进展 [J ] . 节能， 2024 ， 43 ( 1 ): 116 - 118 .

JIAO Jian ， CHEN Binjian ， DIAO Wenpeng ， et al . Research progress on hydrogen production technology by methane steam reforming [J ] . Energy Conservation ， 2024 ， 43 ( 1 ): 116 - 118 .

谭力犁 . 钙铜耦合吸附强化甲烷水蒸气重整制氢的过程分析及材料基础研究 [D ] . 重庆 : 重庆大学， 2018 .

TAN Lili . Study on process analysis and materials behavior in Ca-Cu chemical looping for high-purity H 2 production [D ] . Chongqing : Chongqing University ， 2018 .

曹小敏，李琦，徐亮 . 基于文献计量学的制氢与CCUS技术耦合研究现状及趋势分析 [J ] . 高校地质学报， 2023 ， 29 ( 1 ): 110 - 119 .

CAO Xiaomin ， LI Qi ， XU Liang . Current research status and tendency of hydrogen production coupled CCUS technology based on bibliometrics [J ] . Geological Journal of China Universities ， 2023 ， 29 ( 1 ): 110 - 119 .

牛俊天 . 基于Pt/助剂改性的Ni催化剂CH 4 /CO 2 重整反应机理及特性研究 [D ] . 重庆 : 重庆大学， 2019 .

NIU Juntian . CH 4 /CO 2 reforming over Pt/promotermodified Ni catalyst: Reaction mechanismand characteristics study [D ] . Chongqing : Chongqing University ， 2019 .

纪敏，周美娟，毕颖丽，等 . Ni/γ-Al 2 O 3 ,Ni/MgO,Ni/SiO 2 催化剂上甲烷与二氧化碳重整反应的研究 [J ] . 分子催化， 1997 ，( 1 ): 7 - 13 .

JI Min ， ZHOU Meijuan ， BI Yingli ， et al . Study on the reforming reaction of methane and carbon dioxide over Ni/γ-Al 2 O 3 , Ni/MgO, Ni/SiO 2 catalysts [J ] . Journal of Molecular Catalysis ， 1997 ，( 1 ): 7 - 13 .

张元卓 . 锂基吸附剂在吸附强化甲烷水蒸汽重整制氢中的应用 [D ] . 金华 : 浙江师范大学， 2012 .

ZHANG Yuanzhuo . Lithium-based CO 2 acceptors applied for hydrogen production in sorption-enhanced steam-methane reforming process [D ] . Jinhua : Zhejiang Normal University ， 2012 .

LÓPEZ-ORTIZ A ， RIVERA N G P ， ROJAS A R ， et al . Novel carbon dioxide solid acceptors using sodium containing oxides [J ] . Separation science and technology ， 2005 ， 39 ( 15 ): 3559 - 3572 .

MARTÍNEZ-DLCRUZ L . Cyclic CO 2 chemisorption-desorption behavior of Na 2 ZrO 3 :Structural, microstructural and kinetic variations produced as a function of temperature [J ] . Journal of Solid State Chemistry ， 2013 ， 204 : 298 - 304 .

MENDOZA-NIETO J A ， VERA E ， Pfeiffer H . Methane reforming process by means of a carbonated-Na 2 ZrO 3 catalyst [J ] . Chemistry Letters ， 2016 ， 45 ( 6 ): 685 - 687 .

赵芸蕾 . 化学链CO 2 捕集与CH 4 原位重整制合成气双功能材料构筑及过程优化 [D ] . 长沙 : 湖南大学， 2023 .

ZHAO Yunlei . Construction of dual functional materials and processoptimization on chemical looping CO 2 capture and CH 4 in-situreforming process in syngas production [D ] . Changsha : Hunan University ， 2023 .

HAN Rui ， WANG Yang ， WEI Lifei ， et al . Integrated CO 2 capture and conversion by Cu/CaO dual function materials: Effect of in-situ conversion on the sintering of CaO and its CO 2 capture performance [J ] . Carbon Capture Science & Technology ， 2024 ， 121 : 100220 .

WANG Hao ， LI Rongrong ， WANG Enna ， et al . CO 2 capture and dissociation on novel Ni/CaO bifunctional materials: A theoretical study [J ] . Greenhouse Gases: Science and Technology ， 2024 ， 14 ( 3 ): 411 - 426 .

王菲菲 . Ni/CaO吸收强化甲烷水蒸气重整反应和CO 2 原位转化的DFT模拟研究 [D ] . 济南 : 山东大学， 2023 .

WANG Feifei . Sorption enhanced methane steam reforming using Ni/CaO and in-situ conversion of CO 2 by DFT study [D ] . Jinan : Shandong University ， 2023 .

耿一琪，郭彦霞，樊飙，等 . CaO基吸附剂捕集CO 2 及其抗烧结改性研究进展 [J ] . 燃料化学学报， 2021 ， 49 ( 7 ): 998 - 1013 .

GENG Yiqi ， GUO Yanxia ， FAN Biao ， et al . Research progress of calcium-based adsorbents for CO 2 capture andanti-sintering modification [J ] . Journal of Fuel Chemistry and Technology ， 2021 ， 49 ( 7 ): 998 - 1013 .

CHU Jie ， LIANG Chen ， XUE Wenyan ， et al . Revealing the effect of synthetic method on integrated CO 2 capture and conversion performance of Ni-Na 2 ZrO 3 bifunctional materials [J ] . Separation and Purification Technology ， 2024 ， 346 : 127534 .

DUAN Yuhua . A first-principles density functional theory study of the electronic structural and thermodynamic properties of M 2 ZrO 3 and M 2 CO 3 (M = Na, K) and their capabilities for CO 2 capture [J ] . Journal of Renewable and Sustainable Energy , 2012 ， 4 ( 1 ): 013109 .

宋淑贵 . 高性能硅基负极的结构设计及其稳定性机制研究 [D ] . 南京 : 东南大学， 2021 .

SONG Shugui . Structure design and stability mechanism of high-performance silicon-based anodes [D ] . Nanjing : Southeast University ， 2021 .

WANG Wenju ， FAN Lili ， WANG Guoing ， et al . CO 2 and SO 2 sorption on the alkali metals doped CaO (1 0 0) surface: A DFT-D study [J ] . Applied Surface Science , 2017 ， 425 : 972 - 977 .

OU Zhiliang ， RAN Jingyu ， NIU Juntian ， et al . Effect of active site and charge transferon methane dehydrogenation over different Co doped Ni surfaces by density functionaltheory [J ] . International Journal of Hydrogen Energy , 2020 ， 45 ( 56 ): 31849 - 31862 .

Trimm D L . Coke formation and minimisation during steam reforming reactions [J ] . Catalysis Today ， 1997 ， 37 ( 3 ): 233 - 238 .

张晨鼎 . 碳酸钠和碳酸氢钠及其复盐与水合物的晶体结构 [J ] . 纯碱工业， 2010 ，( 6 ): 3 - 10 .

ZHANG Chending . Crystal structures of sodium carbonate, sodium bicarbonate, their double salts, and hydrates [J ] . Soda Industry ， 2010 ，( 6 ): 3 - 10 .

蔡天意 . 高效钠基脱碳吸收剂开发及反应机理研究 [D ] . 南京 : 东南大学， 2020 .

CAI Tianyi . R & D for an efficient sodiun-based CO 2 solid sorbent and study on its bicarbonation/regeneration mechanism [D ] . Nanjing : Southeast University , 2021 .

BENGAARD H S ， NARSKOV J K ， SEHESTED J ， et al . Steam reforming and graphite formation on Ni catalysts [J ] . Journal of Catalysis , 2002 ， 209 ( 2 ): 365 - 384 .

WANG Shengguang ， CAO Dongbo ， LI Yongwang ， et al . Reactivity of surface OH in CH 4 reforming reactions on Ni (1 1 1): A density functional theory calculation [J ] . Surface Science ， 2009 ， 603 ( 16 ): 2600 - 2606 .

PISTONESI C ， JUAN A ， LRIGOYEN B ， et al . Theoretical and experimental study of methane steam reforming reactions over nickel catalyst [J ] . Applied Surface Science ， 2007 ， 253 ( 9 ): 4427 - 4437 .

LEE Sehyun ， JANG Juehyuk ， JANG lnjoon ， et al . Developmentof robust Pt shell through organic hydride donor in Co-Pt core-shell electrocatalystsfor highly stable proton exchange membrane fuel cells [J ] . Journal of Catalysis ， 2019 ， 379 : 112 - 120 .

李红泰，郭鹏，安立宝 . 硼掺杂碳纳米管吸附硫污染物性能及机理的DFT研究 [J/OL ] . 材料导报 , 1 - 12 [ 2024-09-03 ] . http://kns.cnki.net/kcms/detail/50.1078.TB.20240821.0955.016.html http://kns.cnki.net/kcms/detail/50.1078.TB.20240821.0955.016.html .

LI Hongtai ， GUO Peng ， AN Libao . DFT study on the performance and mechanism of adsorption of sulfide pollutants on boron-doped carbon nanotubes [J/OL ] . Materials Reports ， 1 - 12 [ 2024-09-03 ] . http://kns.cnki.net/kcms/detail/50.1078.TB.20240821.0955.016.html http://kns.cnki.net/kcms/detail/50.1078.TB.20240821.0955.016.html .

杨燕，王献朗，陈昊天，等 . 二维金属有机框架电子性质的电场调控：第一性原理研究 [J/OL ] . 人工晶体学报， 1 - 10 [ 2024-09-13 ] . https://doi.org/10.16553/j.cnki.issn1000-985x.20240829. 010 https://doi.org/10.16553/j.cnki.issn1000-985x.20240829.010 .

YANG Yan ， WANG Xianlang ， CHEN Haotian ， et al . Electric field modulated electronic properties of two-dimensional metal-organic framework: first-principles study [J/OL ] . Journal of Synthetic Crystals , 1 - 10 [ 2024-09-13 ] . https://doi.org/10.16553/j.cnki.issn1000-985x.20240829.010 https://doi.org/10.16553/j.cnki.issn1000-985x.20240829.010 .

XUE Ying ， XU Dingguo ， XIE Daiqian ， et al . Density functional theory studies on tautomeric stability and infrared spectra of 2-chloroadenine [J ] . Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy ， 2000 ， 56 ( 10 ): 1929 - 1938 .

董璐 . 燃煤烟气磁性吸附剂脱汞性能及机理研究 [D ] . 南京 : 东南大学， 2021 .

DONG Lu . Research on the performance and mechanism of mercury removal by magnetic sorbent from coal-fired flue gas [D ] . Nanjing : Southeast University ， 2021 .

孙志杰，史培阳，范蕾 . 氯化钠对石膏晶体生长习性影响的分子动力学模拟 [J ] . 东北大学学报(自然科学版) ， 2023 ， 44 ( 4 ): 524 - 529+535 .

SUN Zhijie ， SHI Peiyang ， FAN Lei . Molecular dynamics simulation on effect of sodium chloride on growth habit of gypsum crystal [J ] . Journal of Northeastern University(Natural Science) ， 2023 ， 44 ( 4 ): 524 - 529+535 .

强龙 . 跨尺度分子筛上苯与乙烯烷基化的催化反应理论研究 [D ] . 青岛 : 青岛科技大学， 2014 .

QIANG Long . The research of the alkylation of benzene and ethylene on the multi-scale zeolites [D ] . Qingdao : Qingdao University of Science and Technology ， 2014 .

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