Tailoring Cation Charge-to-Size Ratios in Zeolite Y for High-performance Methane/Nitrogen Separation

doi:10.1007/s40242-026-5270-6

Chemical Research in Chinese Universities ›› 2026, Vol. 42 ›› Issue (1): 158-166.doi: 10.1007/s40242-026-5270-6

• Research Articles • Previous Articles Next Articles

Tailoring Cation Charge-to-Size Ratios in Zeolite Y for High-performance Methane/Nitrogen Separation

TAO Zeyu^1,2, TIAN Yuanmeng^1,2, SHANG Shanshan^1,2, BELMABKHOUT Youssef³, SHANG Jin^1,2,4

1. City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057, P. R. China;
2. School of Energy and Environment, City University of Hong Kong, Kowloon, Hong Kong 999077, P. R. China;
3. Applied Chemistry and Engineering Research Centre of Excellence (ACER CoE), Mohammed VI Polytechnic University (UM6P), Lot 660, Hay Moulay Rachid, Ben Guerir 43150, Morocco;
4. Low-carbon and Climate Impact Research Center, School of Energy and Environment, City University of Hong Kong, Kowloon, Hong Kong 999077, P. R. China

Received:2025-11-07 Online:2026-02-01 Published:2026-01-28
Contact: SHANG Jin,E-mail:jinshang@cityu.edu.hk;BELMABKHOUT Youssef,E-mail:youssef.belmabkhout@um6p.ma E-mail:jinshang@cityu.edu.hk;youssef.belmabkhout@um6p.ma
Supported by:
This work was supported by the Project of the Science and Technology Innovation Commission of Shenzhen Municipality, China (No. JCYJ20240813153123031) and the Research Grants Council of Hong Kong, China (Nos. CityU 11317722, 11310223, 11313125).

Abstract

Abstract: Low-concentration methane (CH₄) resources, such as coalbed methane (CBM) and coal mine methane (CMM), represent a vast but underutilized source of clean energy, primarily due to the difficulty in separating CH₄ from nitrogen (N₂). Adsorptive separation offers a promising pathway, yet conventional adsorbents suffer from limited selectivity. Here, we report a substantial improvement in the CH₄/N₂ selectivity of large-pore FAU zeolites by modulating their cations with smaller charge-tosize ratios. Combined analyses of adsorption isotherms, isosteric heats, and density functional theory (DFT) binding energies reveal that this strategy suppresses N₂ adsorption by weakening gascation electrostatic interactions, while concurrently enhancing CH₄ uptake through confinement effects that enable a CH₄ molecule to interact with multiple cations. By leveraging this strategy, Cs/TMA-Y, incorporating the cations featuring the smallest charge-to-size ratio in this study (cesium: C^s+ and tetramethylammonium: TMA+), exhibited the highest CH₄/N₂ separation factor under both static and dynamic conditions, along with excellent reusability. Notably, Cs/TMA-Y also delivered the highest CH₄/N₂ selectivity (7.5) reported to date under dynamic binary conditions (50/50, vomlue ratio). Process simulations further identified vacuum swing adsorption (VSA) as the most effective operational mode, highlighting the practical potential of this material. This study establishes a mechanistic framework for cation-controlled CH₄/N₂ separation and provides new design principles for zeolitic adsorbents targeting efficient methane upgrading. Furthermore, this strategy opens a promising pathway to enhance confinement effects in medium- and large-pore zeolites, extending their applicability to a broad range of adsorption- and catalysis-related applications.

Key words: Methane upgrading, Greenhouse gas valorization, Adsorptive CH₄/N₂ separation, Zeolite, Cation charge-to-size ratio

TAO Zeyu, TIAN Yuanmeng, SHANG Shanshan, BELMABKHOUT Youssef, SHANG Jin. Tailoring Cation Charge-to-Size Ratios in Zeolite Y for High-performance Methane/Nitrogen Separation[J]. Chemical Research in Chinese Universities, 2026, 42(1): 158-166.

References

[1] Wang X., Zhou F., Ling Y., Xiao Y., Ma B., Ma X., Yu S., Liu H., Wei K., Kang J., Energy & Fuels, 2021, 35, 15398.
[2] Lu Y. Y., Zhang H. D., Zhou Z., Ge Z. L., Chen C. J., Hou Y. D., Ye M. L., Energy & Fuels, 2021, 35, 9102.
[3] Mar K. A., Unger C., Walderdorff L., Butler T., Environmental Science & Policy, 2022, 134, 127.
[4] Chen S.-J., Yu B.-Y., Journal of the Taiwan Institute of Chemical Engineers, 2021, 127, 56.
[5] Shen J., Wang X., Chen Y., The Canadian Journal of Chemical Engineering, 2023, 101, 7115.
[6] Wei X., Xia Y., Wei S., Chen Y., Yang S, Nanomaterials, 2025, 15, 208.
[7] Su D., Chen P., Li C., Yan Y., Zhao R., Yue Q., Qiao Y, Molecules, 2024, 29, 4404.
[8] Pérez-Botella E., Valencia S., Rey F., Chemical Reviews, 2022, 122, 17647.
[9] Maurin G., Belmabkhout Y., Pirngruber G., Gaberova L., Llewellyn P., Adsorption, 2007, 13, 453.
[10] Pirngruber G. D., Raybaud P., Belmabkhout Y., Čejka J., Zukal A., Physical Chemistry Chemical Physics, 2010, 12, 13534.
[11] Pillai R. S., Sethia G., Jasra R. V., Industrial & Engineering Chemistry Research, 2010, 49, 5816.
[12] Wu Y., Yuan D., Zeng S., Yang L., Dong X., Zhang Q., Xu Y., Liu Z., Fuel, 2021, 301, 121077.
[13] Tao Z., Tian Y., Hanif A., Chan V., Gu Q., Shang J., Carbon Capture Science & Technology, 2023, 8, 100126.
[14] Tao Z., Tian Y., Ou S. Y., Gu Q., Shang J., AIChE Journal, 2023, 69, e18139.
[15] Tao Z., Tian Y., Wu W., Liu Z., Fu W., Kung C.-W., Shang J., NPJ Materials Sustainability, 2024, 2, 20.
[16] Tao Z., Tian Y., Wang R., Zhang T., Wang T., Zhang H., Li M., Qiao J., Kong M., Feng S., Ning Z., Wang H., Gu Q., Shang J., Nature Communications, 2025, 16, 10102.
[17] Myers A. L., Prausnitz J. M., AIChE Journal, 1965, 11, 121.
[18] Lee S., Lee J. H., Kim J., Korean Journal of Chemical Engineering, 2018, 35, 214.
[19] Sayari A., Belmabkhout Y., Materials, Methods and Systems for Selective Capture of CO₂ at High Pressure, US8361200B2, 2013.
[20] Sircar S., Mohr R., Ristic C., Rao M. B., The Journal of Physical Chemistry B, 1999, 103, 6539.
[21] Vidal N. C., Volzone C., Applied Clay Science, 2009, 45, 227.
[22] Shang H., Li Y., Liu J., Tang X., Yang J., Li J., Chinese Journal of Chemical Engineering, 2019, 27, 1044.
[23] Yang J., Tang X., Liu J., Wang J., Shang H., Wu L., Li J., Deng S., Chemical Engineering Journal, 2021, 406, 126599.
[24] Tang X., Liu J., Shang H., Wu L., Yang J., Microporous and Mesoporous Materials, 2020, 297, 110036.
[25] Sadeghi Pouya E., Farmahini A. H., Sadeghi P., Peikert K., Sarkisov L., May E. F., Arami-Niya A., Chemical Engineering Science, 2024, 289, 119819.
[26] Li J.-R., Kuppler R. J., Zhou H.-C., Chemical Society Reviews, 2009, 38, 1477.
[27] Dong Z., Li B., Shang H., Zhang P., Chen S., Yang J., Zeng Z., Wang J., Deng S., AIChE Journal, 2021, 67, e17281.
[28] Liu P., Fan L., Li J., Wu Z., Wang Y., Chen Y., Gao J., Yang J., Li J., Chen B., Li L., Chemistry of Materials, 2024, 36, 2925.
[29] Li Y., Wang Y., Li X., Zhang Y., Wang X., Li J., Yang J., Separation and Purification Technology, 2025, 354, 128719.
[30] Liu J., Shang H., Yang J., Wang J., Li J., Deng S., Chemical Engineering Journal, 2021, 426, 130163.
[31] Lu B., Shen Y., Tang Z., Zhang D., Chen G., Chinese Journal of Chemical Engineering, 2021, 32, 264.
[32] Qadir S., Li D., Gu Y., Yuan Z., Zhao Y., Wang S., Wang S., Chemical Engineering Journal, 2021, 408, 127238.
[33] Bae Y.-S., Snurr R. Q., Angewandte Chemie International Edition, 2011, 50, 11586.
[34] Liu Q., Pham T., Porosoff M. D., Lobo R. F., ChemSusChem, 2012, 5, 2237.

Tailoring Cation Charge-to-Size Ratios in Zeolite Y for High-performance Methane/Nitrogen Separation

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	YANG Jiaqi, CHEN Huanhao, PAN Run, FAN Xiaolei, OU Xiaoxia, Colin SNAPE, HE Jun. Zeolites in CO₂ Hydrogenation: Multifunctional Roles and Advanced Modifications [J]. Chemical Research in Chinese Universities, 2026, 42(1): 3-17.
[2]	ZHOU Hexun, XUE Qiangqiang, HUANG Jun. Solid-state NMR Investigation of Zeolite Catalysts [J]. Chemical Research in Chinese Universities, 2026, 42(1): 18-32.
[3]	CHEN Weiling, XU Li, FU Zhiming, MA Fei, JIANG Jiuxing. Zeolite, a New Intrinsic Pickering Emulsifier [J]. Chemical Research in Chinese Universities, 2026, 42(1): 33-42.
[4]	GONG Liangliang, GONG Xianchen, YIN Jinpeng, LI Xintong, WU Peng, XU Hao. Two-dimensional Organic-Inorganic Ti-MWW as Regenerable Catalyst for Fixed-bed Propylene Epoxidation [J]. Chemical Research in Chinese Universities, 2026, 42(1): 84-93.
[5]	FAN Kai, WU Zihan, LIU Shuo, WU Qinming, ZHANG Weiping, MENG Xiangju, XIAO Feng-Shou. Direct Synthesis of ITR Zeolites with Different Compositions for the Conversion of Methanol to Propylene [J]. Chemical Research in Chinese Universities, 2026, 42(1): 105-110.
[6]	MA Zhonglin, LI Lingyi, HE Ke, ZHANG Wenqi, PENG Fu, SONG Wanrong, HE Linwei, JIANG Zhen, LI Jie, CHEN Long, WANG Shuao. Nitrogen-functionalized Zeolites for Enhanced Cobalt Decontamination [J]. Chemical Research in Chinese Universities, 2026, 42(1): 111-117.
[7]	LI Junze, WANG Yongxiang, BAO Han, ZENG Shuangqin, GAO Xiuzhi, HE Xiaowu, ZHENG Mingji, FENG Ningdong, WANG Qiang, XU Jun, DENG Feng. Probing Framework Boron Speciation and Spatial Distribution in MFI Zeolites by Solid-state NMR [J]. Chemical Research in Chinese Universities, 2026, 42(1): 134-142.
[8]	SHENG Zhizheng, ZHOU Jian, YE Zhaoqi, WANG Tingting, WANG Weihua, WANG Yangdong, TENG Jiawei, XIE Zaiku. Surface Diffusion Regulation of NanoZSM-5 for Catalysis Promotion on Methanol-to-propene [J]. Chemical Research in Chinese Universities, 2026, 42(1): 151-157.
[9]	CHEN Yaxin, LI Lin, WANG Jiaze, LI Yi. Impact of Al Distribution on Ethylene/Ethane Selective Separation over Aluminosilicate Zeolites: A High-throughput Theoretical Study [J]. Chemical Research in Chinese Universities, 2026, 42(1): 167-175.
[10]	YE Junqing, CHENG Bin, LI Xibao, LI Sixian, CHEN Shengchun, QIAN Junfeng, CHEN Qun. Enhanced Decarboxylative Sulfonylation of Cinnamic Acids to (E)-Vinyl Sulfones via Manganese-doped Mesoporous Beta Zeolite Catalyst [J]. Chemical Research in Chinese Universities, 2026, 42(1): 263-275.
[11]	WANG Guowei, XIONG Hao, WEI Fei, CHEN Xiao. Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ [J]. Chemical Research in Chinese Universities, 2025, 41(2): 196-210.
[12]	XU Jing, ZHANG Rui, WANG Ke, WANG Xiao, SONG Shuyan, ZHANG Hongjie. Co-loading Pd and CeO₂ on Silicalite-1 as High-performance Catalyst for Methane Dry Reforming Reaction [J]. Chemical Research in Chinese Universities, 2025, 41(1): 15-20.
[13]	HU Chao, FU Wenhua, YUAN Zhiqing, LIU Chuang, WANG Zhendong, YANG Weimin. Direct Synthesis of UOS Zeolite Using a Simple and Commercially Available Organic Structure-directing Agent [J]. Chemical Research in Chinese Universities, 2025, 41(1): 113-120.
[14]	SHEN Xueyuan, QI Guodong, LIANG Jiawei, WANG Ruichen, XU Jun, DENG Feng. Unveiling the Mechanism of Glycerol Oxidation to Lactic Acid on Pt/Sn-MFI Zeolite: an In situ Solid-state NMR Study [J]. Chemical Research in Chinese Universities, 2024, 40(6): 935-942.
[15]	HUANG Yitong, WANG Yaquan, LIU Wenrong, BU Lingzhen, QU Liping, CHU Kailiang, GUO Niandong, ZHANG Xian, SU Xuemei, LI Yaoning, SANG Juncai. Synthesis of LSX Using Seed-iteration Approach with High N₂ Adsorption Capacity for Air Separation [J]. Chemical Research in Chinese Universities, 2024, 40(6): 1192-1200.