Ultrathin ZSM-5 zeolite nanocrystals synthesized from purely inorganic precursors

doi:10.1016/S1872-2067(26)65176-5

Chinese Journal of Catalysis ›› 2026, Vol. 89: 464-476.DOI: 10.1016/S1872-2067(26)65176-5

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Ultrathin ZSM-5 zeolite nanocrystals synthesized from purely inorganic precursors

Jiaqi Zhao^a, Peiyu Shen^a, Zhengxing Qin^a^,^*(), Camille Longue^b, Nourrdine Chaouati^b, Ruizhe Zhang^b, Xiao Chen^c, Shunsuke Asahina^d^,^e, Natsuko Asano^d^,^e, Gabriel Rueff^b, Eddy Dib^b, Hongman Sun^a, Libin Kang^g, Jiujiang Wang^h, Hongjuan Zhao^h, Honghai Liu^h, Shutao Xuⁱ, Ludovic Pinard^b, Zifeng Yan^a, Svetlana Mintova^a^,^b^,^*()

^aState Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^bUniversité de Caen Normandie, ENSICAEN, CNRS, LCS,Laboratoire Catalyse et Spectrochimie, 14000 Caen, France
^cBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
^dSM Application planning group, JEOL Ltd., Akishima, Tokyo 196-8558, Japan
^eAdvanced Material Analysis Co-creation Research Center, Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Japan
^fDepartment of Applied Chemistry for Environment, Graduate School of Urban Environmental Sci-ences, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan
^gShandong Kehan Silicon Source New Material Co.,Ltd. Linyi 276000, China
^hPetrochemical Research Institute, PetroChina Company Limited, Beijing 100195, China
ⁱNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2026-02-10 Accepted:2026-04-07 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:zhengxing.qin@upc.edu.cn(Z. Qin),svetlana.mintova@ensicaen.fr(S. Mintova).
Supported by:
National Natural Science Foundation of China(22472202);National Natural Science Foundation of China(22178389);Liaoning International Joint Laboratory Project(2024JH2/102100005);PetroChina(KYWX-22-012);PetroChina(KYWX-22-017);PetroChina(KYWX-24-003)

Abstract

Abstract:

Ultrathin zeolite nanocrystals offer distinct advantages in catalysis, adsorption, and separation due to their enhanced exposure of crystal facets and improved molecular diffusion. The synthesis of ultrathin zeolites via template-free and additive-free approaches is highly desirable for sustainable and scalable production, yet remains a longstanding challenge. ZSM-5 nanosheets with a b-axis thickness as small as 10 nm were synthesized via seed-assisted crystallization in a purely inorganic aluminosilicate medium, without the use of organic templates, fluoride, or other additives. The influence of Silicalite-1 seed treatment history, a previously overlooked parameter on ZSM-5 crystallization was systematically investigated. The presence or absence of occluded organic template within the seeds critically modulates crystal morphology by affecting surface dissolution and secondary nucleation at the seed surface. Catalytic testing in methanol conversion indicates that, although structural variations due to nanoscale dimensions are minimal, differences in crystal morphology significantly influence catalytic selectivity. These findings underscore the crucial role of morphology control in tailoring the catalytic performance of zeolites.

Key words: ZSM-5 nanosheets, Seed assisted synthesis, Silicalite-1 zeolite, Morphology control, Methanol to olefins

Jiaqi Zhao, Peiyu Shen, Zhengxing Qin, Camille Longue, Nourrdine Chaouati, Ruizhe Zhang, Xiao Chen, Shunsuke Asahina, Natsuko Asano, Gabriel Rueff, Eddy Dib, Hongman Sun, Libin Kang, Jiujiang Wang, Hongjuan Zhao, Honghai Liu, Shutao Xu, Ludovic Pinard, Zifeng Yan, Svetlana Mintova. Ultrathin ZSM-5 zeolite nanocrystals synthesized from purely inorganic precursors[J]. Chinese Journal of Catalysis, 2026, 89: 464-476.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65176-5

https://www.cjcatal.com/EN/Y2026/V89/I10/464

Figures/Tables 6

Fig. 1. SEM (a-j) and TEM (k-o) images showing the crystal size and morphology of ZSM-5 zeolites synthesized using Silicalite-1 seeds in the presence or absence of tetrapropylammonium cations: (a,f,k) Z1 zeolite synthesized using S1; (b,g,l) Z2 zeolite synthesized using S2; Z3 zeolite synthesized using S3 (c,h,m); Z4 (d,i,n) and Z5 (e,j,o) zeolites synthesized using S4 and S5, respectively.

Fig. 2. HAADF-STEM images and corresponding elemental maps of ZSM-5 zeolite samples: Z1 (a), Z2 (b), Z3 (c), Z4 (d), and Z5 (e).

Table 1 Acidic properties and catalytic descriptor values obtained from n-hexane and 3-methylpentane cracking (initial activity, turnover frequency, paraffin-to-olefin ratio, and constraint index).

	[PyH⁺] ^a	[PyL] ^a	EFAls (δ = 0) ^b	A₀ (n-hex) ^c	TOF (n-hex) ^c	P/O (n-hex) ^c	A₀ (3-MP) ^d	TOF (3-MP) ^d	P/O (3-MP) ^d	CI ^e
Unit	µmol·g_cat^-1	µmol·g_cat^-1	%	mmol·h^-1·g_cat^-1	h^-1	mol/mol	mmol·h^-1·g_cat^-1	h^-1	mol/mol
Z_ref	335	21	4.6	129	384	0.52	169	504	0.20	0.76
Z1	305	135	13.5	246	1001	0.54	384	1560	0.15	0.46
Z2	318	186	14.1	315	1000	0.42	770	2444	0.14	0.41
Z3	357	181	15.9	329	1000	0.46	738	2242	0.14	0.45

Fig. 3. (a) MeOH and DME conversion over the TOS. Cumulative products selectivity and E/P ratio at 100% conversion of MeOH and DME at the initial time (b), 100% conversion before deactivation (c), and 18%-20% iso-conversion and deactivation conditions (d). Black crosses corresponding to conversions on products selectivity. Reaction conditions: 723 K, WHSV: 2.1 g CH3OH gcat-1 h-1; N2/CH3OH = 23 and Ptotal =1 atm.

Fig. 4. Schematic illustration of hydroxyl group adsorption on (010) (a,c) and (100) (b,d) surfaces of MFI zeolite structure. The adsorption modeling was performed without (a,b) and with (c,d) TPA+ occluded.

Fig. 5. SEM (a,d,g) and TEM (b,c,e,f,h,i) images of ZSM-5 zeolites synthesized with varied OH-/SiO2 ratios following the procedure applied for Z3 sample: (a,b,c) Z3-0.33, (d,e,f) Z3-0.3, (g,h,i) Z3-0.25; the suffix corresponds to the respective OH-/SiO2 ratios. (j) SEM and (k,l) TEM images of ZSM-5 zeolite synthesized using 20 nm-sized calcined Silicalite-1 as seeds.

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Ultrathin ZSM-5 zeolite nanocrystals synthesized from purely inorganic precursors

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