分子筛内累积碳物种的动态限域作用

doi:10.1016/S1872-2067(25)64920-5

催化学报 ›› 2026, Vol. 84: 74-79.DOI: 10.1016/S1872-2067(25)64920-5

分子筛内累积碳物种的动态限域作用

叶艺涵^a^,^b, 丁一伦^a^,^b, 彭涛^a^,^b, 刘成^a^,^b, 李昕哲^a^,^b, 赵勇智^a^,^b, 肖建平^a^,^b(), 焦峰^a^,^b(), 潘秀莲^a^,^b

^a 中国科学院大连化学物理研究所, 催化国家重点实验室, 能源催化转化全国重点实验室, 2011-能源材料化学合作创新中心, 辽宁大连 116023
^b 中国科学院大学, 北京 100049

收稿日期:2025-08-28 接受日期:2025-10-16 出版日期:2026-05-18 发布日期:2026-04-16
通讯作者: *电子信箱: xiao@dicp.ac.cn (肖建平),
jiaofeng@dicp.ac.cn (焦峰).
基金资助:
国家重点研发计划(2023YFA1509100);国家重点研发计划(2021YFA1500702);国家重点研发计划(2023YFB4103700);国家自然科学基金(22272167);国家自然科学基金(22321002);何享健青年科学家项目(HERF2025015);中国科学院大连化学物理研究所创新基金(DICP I202424);辽宁省科学基金(2024JH3/10200013);辽宁省科学基金(XLYC2403204);大连市科学基金(2023RG002)

Role of accumulated carbonaceous species on dynamic confinement in zeolite catalysis

Yihan Ye^a^,^b, Yilun Ding^a^,^b, Tao Peng^a^,^b, Cheng Liu^a^,^b, Xinzhe Li^a^,^b, Yongzhi Zhao^a^,^b, Jianping Xiao^a^,^b(), Feng Jiao^a^,^b(), Xiulian Pan^a^,^b

^a State Key Laboratory of Catalysis, National Laboratory for Clean Energy, 2011-Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^b University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-08-28 Accepted:2025-10-16 Online:2026-05-18 Published:2026-04-16
Contact: * E-mail: xiao@dicp.ac.cn (J. Xiao),
jiaofeng@dicp.ac.cn (F. Jiao).
Supported by:
National Key Research and Development Program of China(2023YFA1509100);National Key Research and Development Program of China(2021YFA1500702);Ministry of Science and Technology of China(2023YFB4103700);National Natural Science Foundation of China(22272167);National Natural Science Foundation of China(22321002);He Xiangjian Science Foundation(HERF2025015);Innovation Research Fund of Dalian Institute of Chemical Physics(DICP I202424);Liaoning Natural Science Foundation(2024JH3/10200013);Liaoning Natural Science Foundation(XLYC2403204);Dalian Science and Technology Innovation Fund(2023RG002)

摘要/Abstract

摘要：

空间限域效应是多相催化的关键因素, 可稳定纳米颗粒、调节吸附强度并改变反应路径. 吸附作为反应起始步骤, 其能量变化受限域环境显著影响, “限域能”可量化此类效应并预测催化活性. 在氧化物-分子筛(OXZEO)催化体系中, 分子筛限域酸位点催化的烯烃加氢副反应直接影响合成气转化产物分布. 研究表明, 抑制该加氢反应不仅能提高低碳烯烃选择性, 还可打破活性-选择性权衡限制, 但分子筛调控加氢的机理尚未明确. 实验发现, 合成气反应初期分子筛加氢活性的动态演变与限域碳物种相关, 尽管积碳通常导致催化剂失活, 但其在诱导期的初始积累反而能提高烯烃选择性. 目前, 积碳对传质扩散的影响已受到关注, 但碳物种如何通过动态限域效应影响反应路径的机制仍需深入探究.

本文以MCM-22分子筛为模型, 通过密度泛函理论计算量化了限域效应对乙烯加氢副反应的影响, 建立了碳物种尺寸, 限域能和乙烯选择性之间的关系. 首先, 在Al₁-OH-Si₂, Al₈-OH-Si₈, Al₅-OH-Si₇三种Brönsted酸位点上分别计算了乙烯的吸附能和乙烯加氢能垒, 证明强Brönsted酸位点能促进乙烯吸附, 同时降低加氢能垒, 乙烯的吸附强度与加氢活性呈正相关. 电子局域化函数(ELF)分析进一步阐明, 与气相乙烯分子相比, 吸附的乙烯经历了显著的极化. 在乙烯加氢过渡态, 分子筛中产生C₂H₅⁺和Al-O^‒-Si物种, 这些物种能极化H₂并促进H‒H键断裂. 对乙烯加氢过渡态的电荷分析证明, 较弱的酸位点会抑制H₂极化, 即H⁺的电荷转移量从0.16 e^‒减少(Al₅-O^‒-Si₇位点)至0.13 e^‒ (Al₁-O^‒-Si₂位点), 而H^‒的电荷转移量从0.08 e^‒下降至0.02 e^‒. 较弱的乙烯吸附位点附近H₂极化的减弱会导致加氢能垒升高, 因此, 该结果进一步证明, 乙烯的吸附能可以描述过渡态中H₂的极化程度, 并作为乙烯加氢反应的描述符. 然后, 计算了不同尺寸碳物种限域下的乙烯吸附能和乙烯加氢能垒, 随着碳物种尺寸由37.26 Å²增长到58 Å², 其产生的动态限域作用会导致碳物种结构变形和电荷分布的改变, 逐渐削弱乙烯吸附(约0.3 eV)并抬高乙烯加氢能垒(约0.2 eV). 此外, 对于同种碳物种, 分子筛内更小的孔道尺寸(空间位阻较高)会加强限域作用, 进一步抑制乙烯加氢. 以四甲基萘为例, 随着孔道空间的减小, 乙烯吸附的限域能(从0.06到0.18 eV)和乙烯加氢的限域能垒(从0.11到0.51 eV)也会增加, 进一步证明了孔道内有效空间的减小对乙烯加氢反应的抑制作用.

综上, 本文揭示了分子筛中的动态限域效应对乙烯加氢副反应的影响, 这是提高OXZEO催化体系中烯烃选择性的关键途径, 为OXZEO催化剂的优化设计提供了理论依据.

关键词: 氧化物-分子筛, 密度泛函理论, 合成气转化, 乙烯加氢, 限域效应

Abstract:

: Spatially confined microenvironments offer exceptional potential for regulating catalytic activity and selectivity. This study elucidates how the dynamic evolution of carbonaceous species during syngas conversion alters the confined environment within MCM-22 cages. We establish a confinement energy, quantified through ethylene adsorption measurements, as a key descriptor correlating with hydrogenation activity at Brönsted acid sites. As carbonaceous deposits expand in size during syngas reaction, they progressively occupy cage volume and reduce the available space, thereby enhancing confinement energy. Such energy gain universally weakens reactant adsorption, simultaneously suppressing hydrogenation activity and promoting olefin selectivity. Collectively, these findings advance fundamental understanding of dynamic confinement effects and provide valuable insights for further designing high-selectivity catalysts for syngas conversion.

Key words: Oxide-zeolite, Density functional theory, Syngas conversion, Ethylene hydrogenation, Confinement effect

叶艺涵, 丁一伦, 彭涛, 刘成, 李昕哲, 赵勇智, 肖建平, 焦峰, 潘秀莲. 分子筛内累积碳物种的动态限域作用[J]. 催化学报, 2026, 84: 74-79.

Yihan Ye, Yilun Ding, Tao Peng, Cheng Liu, Xinzhe Li, Yongzhi Zhao, Jianping Xiao, Feng Jiao, Xiulian Pan. Role of accumulated carbonaceous species on dynamic confinement in zeolite catalysis[J]. Chinese Journal of Catalysis, 2026, 84: 74-79.

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Fig. 1. Electronic structure analysis of ethylene adsorption on Br?nsted acid sites with varying strengths and their impact on hydrogenation. Optimized adsorption structures of ethylene on Al1-OH-Si2 (a), Al8-OH-Si8 (b), and Al5-OH-Si7 (c) sites (the pink, red, yellow, black, and white spheres represent Al, O, Si, C, and H atoms, respectively). Electron localization functions (ELFs) of isolated ethylene (d) and adsorbed ethylene on Al1-OH-Si2 (e), Al8-OH-Si8 (f), and Al5-OH-Si7 sites (g). (h) Free energy barriers for ethylene hydrogenation as a function of ethylene adsorption energies on three sites. (i) Electron transfer amount (H+ and H?) in the hydrogenation transition state as a function of ethylene adsorption energy. The grey, red, blue, black, and white spheres represent Al, O, Si, C, and H atoms, respectively. The accumulation and loss of charge are shown in yellow and cyan, respectively.

Fig. 2. Electronic structure analysis of carbonaceous species confined in zeolite and their influences on ethylene hydrogenation. Structures of durene (C10) (a), tetramethyl-naphthalene (C14) (b), and dimethyl-anthracene (C16) (c) confined in MCM-22 cages (ethylene adsorbed at Br?nsted acid site). The distances between carbonaceous species and Br?nsted acid sites are marked with red arrows and black numbers. ELFs of these molecules under zeolite confinement (d?f), and in their free state (g?i). (j) Confinement energy of ethylene adsorption on Al1-OH-Si2 site as a function of the charge transfer from the carbonaceous species. (k) Free energy for the initial state and transition state of ethylene hydrogenation (referring to gas-phase ethylene molecules and H2 molecules) over Al1-OH-Si2 with or without carbonaceous species confinement, plotted against the confinement energy of ethylene adsorption.

Fig. 3. Free energy diagrams of ethylene hydrogenation over Br?nsted acid sites of Al1-OH-Si2 (a), Al8-OH-Si8 (b), and Al5-OH-Si7 (c) with or without carbonaceous species confinement (durene (C10), tetramethyl-naphthalene (C14), and dimethyl-anthracene (C16)).

Fig. 4. The confinement effect of carbonaceous species and cage size on ethylene hydrogenation. (a) Confined hydrogenation barrier at Al1-OH-Si2 site as a function of carbonaceous species size (C10, C14, and C16). (b) Confinement energy of ethylene adsorption and confined hydrogenation barrier as functions of the available cage size (the accessible space around the site).

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分子筛内累积碳物种的动态限域作用

Role of accumulated carbonaceous species on dynamic confinement in zeolite catalysis

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