电力科技与环保2025，Vol.41Issue(3)：373-382,10.DOI:10.19944/j.eptep.1674-8069.2025.03.003
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
摘要
Abstract
[Objective]This study aims to elucidate the microscopic reaction mechanism of Ni-Na2ZrO3 bifunctional material in sorption-enhanced methane steam reforming,addressing the challenges of high energy consumption in CO2 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-Na2ZrO3 surface model was constructed to systematically analyze the adsorption energies and competitive adsorption characteristics of 21 adsorbates(including CHx,CHxOH,CO,CO2,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 CO2 formation.Key steps and rate-limiting stages of carbon conversion were identified by integrating surface energy,adsorption energy,and reaction barrier data.Furthermore,the CO2 adsorption-desorption performance of Na2ZrO3 and Ni-Na2ZrO3 was compared to evaluate the impact of Ni doping on material regenerability.[Results]The results indicate that the absolute adsorption energy of CHx and CHxOH 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,H2 exhibits weak adsorption,facilitating its desorption,while CO2 remains stably adsorbed,enabling in-situ separation.The optimal methane dissociation pathway follows direct dehydrogenation(CH4→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-Na2ZrO3 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 CO2capture 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
镍-锆酸钠/双功能材料/吸附增强甲烷蒸汽重整/密度泛函理论Key words
Ni-Na2ZrO3/bifunctional materials/sorption enhanced methane steam reforming/density functional theory分类
能源与动力引用本文复制引用
孙超,谢华清,徐海健,张树,刘坤..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):373-382,10.基金项目
国家自然科学基金项目(52476181) （52476181）
