Research on the mechanism of methane reforming based on Ni-Na<sub>2</sub>ZrO<sub>3</sub> adsorption-catalytic bifunctional material

SUN Chao; XIE Huaqing; XU Haijian; ZHANG Shu; LIU Kun

doi:10.19944/j.eptep.1674-8069.2025.03.003

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Research on the mechanism of methane reforming based on Ni-Na₂ZrO₃ adsorption-catalytic bifunctional material

Green Catalytic Technologies for the Power Sector in a Dual Carbon | 更新时间：2026-10-14

- Research on the mechanism of methane reforming based on Ni-Na₂ZrO₃ adsorption-catalytic bifunctional material
- Electric Power Technology and Environmental Protection Vol. 41, Issue 3, Pages: 373-382(2025)
- 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：
- 基金信息：
- DOI：10.19944/j.eptep.1674-8069.2025.03.003
  CLC： TK02;TQ152
- Received：12 December 2024，
  
  Accepted：10 May 2025，
  
  Published：15 June 2025
- 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

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Research on the mechanism of methane reforming based on Ni-Na2ZrO3 adsorption-catalytic bifunctional material

DOI：10.19944/j.eptep.1674-8069.2025.03.003

摘要

Abstract

关键词

Keywords

references

Research on the mechanism of methane reforming based on Ni-Na₂ZrO₃ adsorption-catalytic bifunctional material