Role of accumulated carbonaceous species on dynamic confinement in zeolite catalysis

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64920-5

https://www.cjcatal.com/EN/Y2026/V84/I5/74

Figures/Tables 4

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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