Precise regulation of acid centers in different cavities of FER-zeolite via selective passivation to identify pentene monomolecular cracking reaction position

doi:10.1016/S1872-2067(25)64887-X

Abstract

Abstract:

Precisely controlling acid center position in zeolites is still challenging. Pentene monomolecular cracking offers an ideal route to maximize ethylene and propylene yields simultaneously. To reveal the relationship between acid site distribution in FER-zeolite and pentene monomolecular cracking activity, this study proposes a novel strategy integrating pyridine pre-adsorption with K⁺ exchange modification to selectively shield acid sites within FER cages, while phosphorus modification is employed to selectively passivate acid sites in 10-MR channels and on the external surface. Adsorption infrared (IR) spectroscopy (CD₃CN-IR, Py-IR, and 2,6-DMPy-IR), and OH-IR characterization verified the selectivity and efficiency of these modification process. FER zeolites with distinct acid site distributions exhibit typical monomolecular cracking characteristics in pentene cracking, where the pentene cracking activity is linearly related to the acid density in the 10-MR channel and independent of the FER cage acidity. This result identifies 10-MR channel as primary pentene monomolecular cracking reaction position for the first time, providing a theoretical basis for designing zeolite catalysts that maximize ethylene and propylene production. The synergistic application of the pre-adsorption-K⁺ exchange modification strategy using different size basic molecules and phosphorus modification will provide an effective approach for precise control of acid site locations in zeolites with diverse pore/cavities architectures.

Key words: FER zeolite, Acid centers, Selective passivation, Pentene monomolecular cracking, Catalytic reaction position

Fang Li, Penghe Zhang, Yiran Wang, Yueming Liu, Mingyuan He. Precise regulation of acid centers in different cavities of FER-zeolite via selective passivation to identify pentene monomolecular cracking reaction position[J]. Chinese Journal of Catalysis, 2026, 81: 136-147.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64887-X

https://www.cjcatal.com/EN/Y2026/V81/I2/136

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Sample	Si/Al₂ (Bulk)^a	K content^a (wt%)	Pore property ^b
Sample	Si/Al₂ (Bulk)^a	K content^a (wt%)	A_micro (m²/g)	A_exter (m²/g)	V_micro (cm³/g)	V_total (cm³/g)
ZSM-35	76	—	277	27	0.123	0.229
ZSM-35-Py	76	—	168	21	0.074	0.212
ZSM-35-Py-C	76	—	283	28	0.123	0.224
Py-0.02K⁺-C	76	0.02	276	25	0.122	0.213
Py-0.04K⁺-C	76	0.04	269	29	0.118	0.221
Py-0.06K⁺-C	76	0.06	270	23	0.118	0.216

Sample	Si/Al₂ (Bulk)^a	K content^a (wt%)	Pore property ^b
Sample	Si/Al₂ (Bulk)^a	K content^a (wt%)	A_micro (m²/g)	A_exter (m²/g)	V_micro (cm³/g)	V_total (cm³/g)
ZSM-35	76	—	277	27	0.123	0.229
ZSM-35-Py	76	—	168	21	0.074	0.212
ZSM-35-Py-C	76	—	283	28	0.123	0.224
Py-0.02K⁺-C	76	0.02	276	25	0.122	0.213
Py-0.04K⁺-C	76	0.04	269	29	0.118	0.221
Py-0.06K⁺-C	76	0.06	270	23	0.118	0.216

Sample	NH₃-TPD ^a (mmol/g)			CD₃CN-IR ^b (mmol/g)	Py-IR ^c (mmol/g)		2,6-DMPy-IR ^d (mmol/g)	BAS in FER cage^e (mmol/g)	Hydroxyl FT-IR ^f
Sample	WA	SA	TA	Total BAS		10-MR and External BAS	External BAS	BAS in FER cage^e (mmol/g)	-OH in 10-MR(%)
ZSM-35	0.119	0.207	0.326	0.290	0.079		0.011	0.211	0.19
ZSM-35-Py	0.099	0.156	0.255	—	—		—	—	—
ZSM-35-Py-C	0.122	0.201	0.323	0.288	0.076		0.011	0.212	0.19
Py-0.02K⁺-C	0.109	0.118	0.227	0.196	0.078		0.010	0.118	0.24
Py-0.04K⁺-C	0.092	0.095	0.187	0.146	0.078		0.009	0.068	0.27
Py-0.06K⁺-C	0.073	0.086	0.159	0.133	0.079		0.011	0.054	0.32

Sample	NH₃-TPD ^a (mmol/g)			CD₃CN-IR ^b (mmol/g)	Py-IR ^c (mmol/g)		2,6-DMPy-IR ^d (mmol/g)	BAS in FER cage^e (mmol/g)	Hydroxyl FT-IR ^f
Sample	WA	SA	TA	Total BAS		10-MR and External BAS	External BAS	BAS in FER cage^e (mmol/g)	-OH in 10-MR(%)
ZSM-35	0.119	0.207	0.326	0.290	0.079		0.011	0.211	0.19
ZSM-35-Py	0.099	0.156	0.255	—	—		—	—	—
ZSM-35-Py-C	0.122	0.201	0.323	0.288	0.076		0.011	0.212	0.19
Py-0.02K⁺-C	0.109	0.118	0.227	0.196	0.078		0.010	0.118	0.24
Py-0.04K⁺-C	0.092	0.095	0.187	0.146	0.078		0.009	0.068	0.27
Py-0.06K⁺-C	0.073	0.086	0.159	0.133	0.079		0.011	0.054	0.32

Sample	Si/Al₂(Bulk) ^a	P content^a(wt%)	Pore properties ^b
Sample	Si/Al₂(Bulk) ^a	P content^a(wt%)	A_micro (m²/g)	A_exter (m²/g)	V_micro (cm³/g)	V_total (cm³/g)
ZSM-35	76	—	277	27	0.123	0.229
0.19P-ZSM-35	76	0.19	252	28	0.113	0.215
0.42P-ZSM-35	76	0.42	241	28	0.107	0.205
0.60P-ZSM-35	76	0.60	240	22	0.107	0.190
0.78P-ZSM-35	76	0.78	233	24	0.102	0.194
1.02P-ZSM-35	76	1.02	210	26	0.093	0.183