碳扩散机制作为有效的稳定性增强策略——以镍基催化剂用于光热催化甲烷干重整为例的研究

doi:10.1016/S1872-2067(24)60249-4

催化学报 ›› 2025, Vol. 70: 399-409.DOI: 10.1016/S1872-2067(24)60249-4

碳扩散机制作为有效的稳定性增强策略——以镍基催化剂用于光热催化甲烷干重整为例的研究

李德正^a^,¹, 刘会敏^a^,^*^,¹(), 肖雪文^b^,¹, 赵曼淇^a, 贺德华^c^,^*(), 雷一鸣^d^,^*()

^a辽宁工业大学化学与环境工程学院, 辽宁锦州 121000, 中国
^b奥赛分子科学研究所(ISMO), 巴黎萨克雷大学和国家科学研究中心(CNRS), 奥赛 91400, 法国
^c清华大学化学系, 有机光电子与分子工程教育部重点实验室, 北京 100084, 中国
^d巴塞罗那自治大学理学院化学系(无机化学), 萨丹约拉, 巴塞罗那 08193, 西班牙

收稿日期:2024-11-04 接受日期:2025-01-19 出版日期:2025-03-18 发布日期:2025-03-20
通讯作者: * 电子信箱: liuhuimin08@tsinghua.org.cn (刘会敏),hedeh@mail.tsinghua.edu.cn (贺德华),yiming.lei@uab.cat (雷一鸣).
作者简介:¹共同第二作者.
基金资助:
国家自然科学基金(21902116);辽宁省青年人才计划(XLYC2203068);辽宁省科技厅科研基金(2022-MS-379);辽宁省教育厅2024年度基本科研业务费专项资金、国家留学基金(202206250016);辽宁省教育厅2024年度基本科研业务费专项资金、国家留学基金(202206020087)

Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane

Dezheng Li^a^,¹, Huimin Liu^a^,^*^,¹(), Xuewen Xiao^b^,¹, Manqi Zhao^a, Dehua He^c^,^*(), Yiming Lei^d^,^*()

^aSchool of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121000, Liaoning, China
^bInstitute of Molecular Sciences of Orsay (ISMO), University Paris-Saclay and National Centre for Scientific Research (CNRS), Orsay, 91400, France
^cKey Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China
^dDepartment of Chemistry (Inorganic Chemistry), Faculty of Sciences, Autonomous University of Barcelona (UAB), Cerdanyola del Valles, Barcelona 08193, Spain

Received:2024-11-04 Accepted:2025-01-19 Online:2025-03-18 Published:2025-03-20
Contact: * E-mail: liuhuimin08@tsinghua.org.cn (H. Liu),hedeh@mail.tsinghua.edu.cn (D. He),yiming.lei@uab.cat (Y. Lei).
About author:¹Contributed to this work equally.
Supported by:
National Natural Science Foundation of China(21902116);Young Talent Plan of Liaoning Province(XLYC2203068);Scientific Research Foundation of Technology Department of Liaoning Province of China(2022-MS-379);2024 Fundamental Research Funding of the Educational Department of Liaoning Province, and the China Scholarship Council is gratefully acknowledged by Y. Lei(202206250016);2024 Fundamental Research Funding of the Educational Department of Liaoning Province, and the China Scholarship Council is gratefully acknowledged by X. Xiao(202206020087)

摘要/Abstract

摘要：

光热催化甲烷干重整(DRM)技术能够在温和条件下将温室气体(CH₄和CO₂)转化为合成气(H₂和CO), 为下游化工提供原料, 对减少温室效应、实现碳中和具有重要意义. 镍(Ni)基催化剂因成本低、催化活性高而备受关注, 在DRM领域得到了广泛研究和应用. 然而, CH₄易在Ni基催化剂表面过度裂解生成沉积碳, 导致催化剂迅速失活, 严重阻碍了其在光热DRM领域的工业化应用, 成为当前亟待解决的关键挑战.

为了提升Ni基催化剂的长期稳定性, 本文提出了一种碳原子扩散策略, 并以锌掺杂镍基催化剂(Ni₃Zn@CeO₂)为例, 探究了该策略对Ni基催化剂活性及稳定性的影响. Ni₃Zn合金相的设计考虑到引入外部金属原子可以有效地调节Ni晶格参数, 从而在间隙位点实现碳原子的扩散. 通过共沉淀法以及在H₂/N₂气氛下的热还原过程制备了CeO₂负载合金化Ni₃Zn. X射线衍射(XRD)、透射电子显微镜和高角环形暗场扫描透射电镜表征证实了合金相Ni₃Zn成功地锚定在CeO₂表面. 为了验证这一策略的有效性并探究其机理, 将Ni₃Zn@CeO₂光热催化剂用于长时间DRM反应. 结果表明, 在光热催化DRM反应中(0.1 g催化剂、500 °C、300瓦氙灯照射), Ni₃Zn@CeO₂具有超过70 h的稳定性, 其光热催化DRM活性是热催化活性的1.2倍. 光热条件下, 初始CH₄和CO₂转化率分别为536.5和543.4 μmol∙g⁻¹∙min⁻¹, H₂和CO的释放速率分别为349和497 μmol∙g⁻¹∙min⁻¹. 机理研究表明, DRM反应效率的提高应归因于光热效应、CO₂强吸附能力和Ni₃Zn@CeO₂强还原能力之间的协同作用. XRD和密度泛函理论(DFT)计算结果证实, 稳定性增强应归因于Ni₃Zn空间半径的增加, 这有利于碳原子扩散到Ni₃Zn八面体中心, 原位形成具有体心立方(bcc)结构的Ni₃ZnC_0.7相, 抑制碳沉积现象, 成功提高了Ni基催化剂的稳定性. 此外, 原位漫反射红外傅里叶变换光谱和DFT计算表明, Ni₃Zn@CeO₂有利于CH₄的活化, 提高了光热催化DRM的反应效率. 碳原子扩散机制可以抑制CH₄过度裂解, 避免催化剂表面的碳沉积问题. 配位的碳原子可以与b-CO₂*中间体相互作用, 实现完整的碳原子扩散-反应循环.

综上所述, 本文通过诱导碳原子在Ni₃Zn晶格内扩散的策略开发了一种具有较好稳定性的光热催化DRM Ni基催化剂. 作为Ni基催化剂的稳定性增强机制, 这种碳原子扩散策略有望扩展到其他光热平台和反应中.

关键词: 光热催化, 甲烷干重整, 镍基催化剂, 稳定性增强, 碳原子扩散

Abstract:

Photothermal catalytic methane dry reforming (DRM) technology can convert greenhouse gases (i.e. CH₄ and CO₂) into syngas (i.e. H₂ and CO), providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality. In the DRM field, Ni-based catalysts attract wide attention due to their low cost and high activity. However, the carbon deposition over Ni-based catalysts always leads to rapid deactivation, which is still a main challenge. To improve the long-term stability of Ni-based catalysts, this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst (Ni₃Zn@CeO₂). The photothermal catalytic behavior of Ni₃Zn@CeO₂ can maintain more than 70 h in DRM reaction. And the photocatalytic DRM activity of Ni₃Zn@CeO₂ is 1.2 times higher than thermal catalytic activity. Density functional theory (DFT) calculation and experimental characterizations indicate that Ni₃Zn promotes the diffusion of carbon atoms into the Ni₃Zn to form the Ni₃ZnC_0.7 phase with body-centered cubic (bcc) structure, thus inhibiting carbon deposition. Further, in-situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and DFT calculation prove Ni₃Zn@CeO₂ benefits the CH₄ activation and inhibits the carbon deposition during the DRM process. Through inducing carbon atoms diffusion within the Ni₃Zn lattice, this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH₄ conversion implementations with long-term stability.

Key words: Photothermal catalysis, Methane dry reforming, Ni-based catalyst, Stability enhancement, Carbon atom diffusion

李德正, 刘会敏, 肖雪文, 赵曼淇, 贺德华, 雷一鸣. 碳扩散机制作为有效的稳定性增强策略——以镍基催化剂用于光热催化甲烷干重整为例的研究[J]. 催化学报, 2025, 70: 399-409.

Dezheng Li, Huimin Liu, Xuewen Xiao, Manqi Zhao, Dehua He, Yiming Lei. Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane[J]. Chinese Journal of Catalysis, 2025, 70: 399-409.

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图/表 6

Fig. 1. Characterizations of phase and structures. (a) XRD patterns of Ni@CeO2 and Ni3Zn@CeO2. HR-TEM (b) and HAADF-STEM images with corresponding EDS mapping (c) of Ni3Zn@CeO2.

Fig. 2. Thermal and photothermal catalytic DRM performances. Conversion rates of CH4 (a) and CO2 (b) over Ni@CeO2 and Ni3Zn@CeO2 under thermal and photothermal conditions during DRM reactions. Reaction conditions: CH4: CO2 = 1:1, temperature: 500 °C, pressure: 1 bar, WHSV: 6 × 103 mL ·min?1·gcat?1, light source: visible light, sample: 0.1 g.

Fig. 3. Characterizations of optical, metal-support interaction, and CO2 absorption properties. (a) UV-vis spectra of CeO2, Ni@CeO2, and Ni3Zn@CeO2. (b) H2-TPR curves of Ni@CeO2 and Ni3Zn@CeO2. (c) CO2-TPD curves of Ni@CeO2 and Ni3Zn@CeO2.

Fig. 4. Stability test of the Ni3Zn@CeO2 catalyst during 70 h DRM reaction. Conversion rates of CH4 and CO2 over Ni3Zn@CeO2 during photothermal catalytic DRM reaction. Reaction conditions: CH4: CO2 = 1: 1, temperature: 500 °C, pressure: 1 bar, WHSV: 6 × 103 mL?min?1?gcat?1, light source: visible light, sample: 0.1 g.

Fig. 5. Characterizations of phase, structures, carbon deposition states, and elemental states of Ni@CeO2 and Ni3Zn@CeO2 after DRM reactions. (a) The XRD pattern of Ni@CeO2, Ni@CeO2-AR, Ni3Zn@CeO2, and Ni3Zn@CeO2-AR. TEM images of Ni@CeO2 (b), Ni@CeO2-AR (c), Ni3Zn@CeO2 (d), and Ni3Zn@CeO2-AR (e). (f) HR-TEM image of Ni3Zn@CeO2-AR. (g) HAADF-STEM images with corresponding EDS mapping of Ni3Zn@CeO2-AR. (h) TGA curves of Ni@CeO2-AR and Ni3Zn@CeO2-AR. (i) XPS spectra of Ni 2p in Ni@CeO2, Ni3Zn@CeO2, and Ni3Zn@CeO2-AR. (j) The structures of Ni3Zn and Ni3ZnC0.7 with face-center cubic and body-center cubic structures.

Fig. 6. Characterization and theoretical studies of DRM reaction mechanism. (a) In-situ DRIFTS spectra of the Ni3Zn@CeO2 catalyst. Operating conditions: 25-500 °C, heating rate: 7 °C min?1, sampling time interval: 5 min, CH4: CO2 = 1: 1, total flow rate: 10 mL·min?1, 0.1 g of catalyst, with visible light irradiation (300 W Xe lamp). (b) Free energy on Ni NPs and Ni3ZnC0.7 during CH4 dissociation steps.

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碳扩散机制作为有效的稳定性增强策略——以镍基催化剂用于光热催化甲烷干重整为例的研究

Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane

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