FER分子筛酸中心的选择性钝化以识别戊烯单分子催化裂解的位置

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

催化学报 ›› 2026, Vol. 81: 136-147.DOI: 10.1016/S1872-2067(25)64887-X

FER分子筛酸中心的选择性钝化以识别戊烯单分子催化裂解的位置

李芳^a, 张鹏鹤^a, 王怡然^a, 刘月明^a^,^b(), 何鸣元^a^,^b()

^a 华东师范大学化学与分子工程学院, 石油化工分子转化与反应工程全国重点实验室, 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
^b 崇明生态研究院, 上海 202162

收稿日期:2025-06-26 接受日期:2025-08-13 出版日期:2026-02-18 发布日期:2025-12-26
通讯作者: *电子信箱: ymliu@chem.ecnu.edu.cn (刘月明),hemingyuan@126.com (何鸣元).
基金资助:
国家自然科学基金(22572055);国家自然科学基金(U24B20200);国家自然科学基金(22072044)

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

Fang Li^a, Penghe Zhang^a, Yiran Wang^a, Yueming Liu^a^,^b(), Mingyuan He^a^,^b()

^a State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
^b Institute of Eco-Chongming, Shanghai 202162, China

Received:2025-06-26 Accepted:2025-08-13 Online:2026-02-18 Published:2025-12-26
Contact: *E-mail: ymliu@chem.ecnu.edu.cn (Y. Liu),hemingyuan@126.com (M. He).
Supported by:
National Natural Science Foundation of China(22572055);National Natural Science Foundation of China(U24B20200);National Natural Science Foundation of China(22072044)

摘要/Abstract

摘要：

以烯烃的生成与转化为纽带, 极大程度强化烯烃的单分子裂解反应路径, 是提高碳资源利用率及C₂⁼和C₃⁼导向生成的化学基础, 其核心是研发酸性质(酸类型、酸量、酸强度和酸位置)精准调控的分子筛催化剂. C₅⁼单分子裂解是实现C₂⁼和C₃⁼同时最大化生成的理想反应, 而FER分子筛被认为是强化该反应的理想活性组分. 为阐明仍未厘清的FER分子筛中酸中心的位置与C₅⁼单分子裂解反应进行场所的构效关系, 精准调控其酸中心空间分布是基础. 然而, 精准调控分子筛酸中心的位置极具挑战性. 为此, 开发FER分子筛酸中心选择性钝化的策略及进一步探究分子筛活性中心位置与C₅⁼单分子裂解反应路径的构效关系, 是烯烃裂解过程研究的焦点.

本文基于分子筛择形基本原理, 利用“分子大小不同、其进入FER分子筛十元环孔道及FER笼的趋势不同”的特性, 选择合适的改性试剂分子实现了FER分子筛中不同位置酸中心的精准调控. 首先, 提出了吡啶预吸附-K⁺交换改性新策略: 先通过吡啶预吸附FER分子筛十元环孔道内酸中心, 再在温和条件下经K⁺交换选择性钝化FER笼内酸中心, 最后高温焙烧脱除吡啶以恢复十元环孔道内的酸中心. 该过程中, 化学吸附的吡啶有效保护十元环孔道及外表面的酸中心, 成功实现FER分子筛中FER笼酸中心的选择性钝化, 且通过调控K⁺交换程度, 可制备FER笼酸中心数目不同、而十元环酸中心几乎不变的改性FER分子筛. 同时, 采用不同浓度的磷酸浸渍改性, 实现FER分子筛十元环孔道的酸中心选择性钝化, 得到FER笼内的酸中心含量稳定、而十元环孔道中的酸中心含量呈梯度变化的改性FER分子筛. NH₃-程序升温脱附、不同大小碱性分子(CD₃CN-IR、Py-IR和2,6-DMPy-IR)的吸附红外和OH-IR的表征结果表明, 吡啶预吸附-K⁺交换改性过程中, 吡啶分子选择性保护了FER分子筛十元环孔道及外表面酸中心, K⁺选择性交换屏蔽了FER笼内酸中心; 而磷改性过程中, 酸中心的选择性屏蔽作用则相反. 进一步探究了FER分子筛活性中心位置与C₅⁼单分子裂解反应路径的构效关系, 结果发现, 酸中心位置分布不同的FER分子筛催化C₅⁼裂解反应均显示出典型的单分子裂解反应特性, 产物丙烯/乙烯(P/E)比均~1、C₂⁼和C₃⁼总选择性均~88%, 且该特性不受FER分子筛酸性质影响. 特别的是, C₅⁼单分子裂解反应活性与十元环孔道中的酸中心含量呈线性正相关, 而与FER笼内的酸中心量无关.

综上, 基于本文发展的改性策略, 通过调节预吸附碱性分子的尺寸, 将为含有不同尺寸孔道/空穴分子筛酸中心位置的精准调控提供有效途径、促进依赖于特定酸中心空间分布的择形催化反应体系高性能分子筛催化剂的设计和研发.

关键词: FER分子筛, 酸中心, 选择性钝化, 戊烯单分子裂解, 催化反应位点

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

李芳, 张鹏鹤, 王怡然, 刘月明, 何鸣元. FER分子筛酸中心的选择性钝化以识别戊烯单分子催化裂解的位置[J]. 催化学报, 2026, 81: 136-147.

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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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

FER分子筛酸中心的选择性钝化以识别戊烯单分子催化裂解的位置

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

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