以Mo-EDTA为钼源直接水热合成Mo-MFI分子筛及其催化环己烯环氧化性能

doi:10.1016/S1872-2067(21)63826-3

摘要/Abstract

摘要：

环氧化物是一种重要的有机化工原料, 广泛应用于合成化学、聚合物合成、食品化学、药物化学等领域中. 烯烃催化环氧化反应是制备环氧化物的主要方法. 一些均相钼配合物催化剂对烯烃环氧化反应表现出较好的催化性能. 然而均相催化剂在实际生产中存在与产物分离困难、不易循环利用等问题. 为解决上述问题, 研究人员采用不同策略将各种钼配合物负载在固体载体上, 制备出活性相对较高的多相钼配合物催化剂. 然而, 这类负载型钼配合物催化剂在以双氧水为氧化剂的反应体系中普遍存在活性组分易于流失的问题, 导致催化剂的稳定性相对较差. 因此,设计制备具有高活性和高稳定性的多相钼基烯烃环氧化催化剂具有重要的科学意义和实用价值. 将过渡金属引入到具有MFI型拓扑结构的微孔分子筛的骨架上能够制备出具有高活性和高稳定性的杂原子分子筛催化剂. 例如, 采用直接水热法合成的钛硅分子筛(如TS-1)对以双氧水为氧化剂的小分子烯烃(如丙烯)环氧化反应表现出非常高的活性和稳定性. 受这一研究结果启发, 研究人员还开展了水热法合成Mo原子取代的MFI型分子筛(Mo-MFI). 然而, 由于Mo的离子半径较大(与Si相比), 且合成体系中的Mo物种在碱性条件下易于发生沉淀, 导致引入到分子筛骨架或孔道中的Mo含量极低.

本文以Mo-EDTA配合物为钼源, 四丙基氢氧化铵为模板剂, 正硅酸乙酯为硅源, 采用一步水热法合成了系列具有不同钼含量的Mo-MFI-n分子筛(n代表初始Si/Mo摩尔比). 结合X-射线粉未衍射、红外光谱、紫外-可见吸收光谱、拉曼光谱、透射电子显微镜等表征技术对分子筛的结构、组成和Mo物种的状态进行了研究. 结果表明, 使用Mo-EDTA作为钼源有利于在分子筛骨架和孔道中引入更多的Mo物种; EDTA^2-独特的配位能力使其在分子筛生长过程中能够有效调节Mo物种的释放率, 并与硅物种缩合的速率匹配, 从而使更多的Mo物种被引入到分子筛骨架中; 同时也会有少量的Mo物种以骨架外Mo团簇的形式分布在分子筛的孔道内或孔口附近. 通过以双氧水为氧化剂的环己烯环氧化反应考察了所制备的Mo-MFI-n催化剂的性能. 经组分优化的Mo-MFI-50(初始Si/Mo摩尔比为50)催化剂能够在较温和的条件下有效地将环己烯转化为相应的环氧化物. 在75 °C下反应9 h后, 环己烯转化率和环氧化物选择性分别高达93%和82%, 性能明显优于传统水热法合成的Mo-MFI分子筛. 此外, 反应后的Mo-MFI-50分子筛催化剂通过简单的过滤而不需要焙烧处理就可多次重复利用, 表现出较高的结构稳定性和循环性.

关键词: MFI分子筛, 钼催化剂, 乙二胺四乙酸, 环己烯, 环氧化

Abstract:

A series of Mo-containing MFI zeolites with different Mo loadings (Mo-MFI-n, n represent the initial Si/Mo molar ratio) was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source. Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites. The special complexing capability of EDTA^2- plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process, thus leading to a uniform distribution of Mo in the MFI framework. In addition, a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites. The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H₂O₂ as the oxidant. The composition-optimized catalyst, Mo-MFI-50, efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion (93%) and epoxide selectivity (82%) at 75 °C after 9 h of reaction. Moreover, the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.

Key words: MFI zeolite, Molybdenum catalyst, Ethylenediamine tetraacetic sodium, Cyclohexene, Epoxidation

张浩洋, 徐丽粉, 常鑫瑜, 缪嵩松, 孙宇婷, 贾明君. 以Mo-EDTA为钼源直接水热合成Mo-MFI分子筛及其催化环己烯环氧化性能[J]. 催化学报, 2021, 42(12): 2265-2274.

Haoyang Zhang, Lifen Xu, Xinyu Chang, Songsong Miao, Yuting Sun, Mingjun Jia. Direct hydrothermal synthesis of Mo-containing MFI zeolites using Mo-EDTA complex and their catalytic application in cyclohexene epoxidation[J]. Chinese Journal of Catalysis, 2021, 42(12): 2265-2274.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63826-3

https://www.cjcatal.com/CN/Y2021/V42/I12/2265

图/表 11

Table 1 Mo contents and texture parameters of various Mo-MFI zeolites.

Sample	Mo content ^a (wt%)	A_BET^b (m²g^-1)	V_micro^c (m³g^-1)	RC ^d (%)
Mo-MFI-200	0.10	345	0.096	88
Mo-MFI-100	0.15	346	0.099	86
Mo-MFI-67	0.21	371	0.096	88
Mo-MFI-50	0.24	376	0.087	85
Mo-MFI-50-ref	0.07	345	0.120	100
Mo-MFI-40	0.32	325	0.116	70
Mo/S-1-ref	0.80	177	0.042	—
Spent Mo-MFI-50 ^e	0.24	365	0.096	—

Fig. 1. XRD patterns of various Mo-MFI zeolites.

Fig. 2. N2 adsorption-desorption isotherms of various Mo-MFI zeolites.

Fig. 3. SEM image of Mo-MFI-50 (a) and corresponding EDS elemental analysis (b) and mapping images: O (c), Si (d), Mo (e).

Fig. 4. TEM (a) and HRTEM (b) images of Mo-MFI-50.

Fig. 5. FT-IR spectra (a) and DRUV-vis spectra (b) of various Mo-MFI samples.

Fig. 6. Raman spectra of various Mo-containing MFI samples.

Table 2 Catalytic performance of various Mo-containing MFI catalysts in the epoxidation of cyclohexene with H2O2 as the oxidant.

Catalyst	Conversion (%)	Selectivity (mol%)				TOF^a
Catalyst	Conversion (%)	epoxide	CyH-ol	CyH-one	diol	(h^-1)
Mo-MFI-200	36.5	84.4	4.3	3.9	7.4	934
Mo-MFI-100	39.9	89.4	3.6	3.3	3.7	681
Mo-MFI-67	41.1	89.3	3.4	4.2	3.1	501
Mo-MFI-50	71.8	84.8	4.9	5.2	5.1	766
Mo-MFI-50-ref	13.5	85.1	4.6	6.0	4.3	494
Mo-MFI-40	42.9	90.2	3.2	4.2	2.4	343
Mo/S-1-ref	11.2	13.9	25.4	35.2	25.5	35.8

Fig. 7. Time-dependent profiles of the catalytic performance of Mo-MFI-50 (a) and Mo-MFI-50-ref (b). Reaction conditions: 20 mmol cyclohexene, 40 mmol H2O2 (30 wt%), 0.3 g catalyst, 5 mL acetonitrile, 75 °C.

Fig. 8. Effect of the reaction temperature on the catalytic performance of Mo-MFI-50. Reaction conditions: 20 mmol cyclohexene, 40 mmol H2O2 (30 wt%), 0.3 g catalyst, 5 mL acetonitrile, and 9 h.

Fig. 9. Recyclability of Mo-MFI-50 for cyclohexene epoxidation. Reaction conditions: 20 mmol cyclohexene, 40 mmol H2O2 (30 wt%), 0.3 g catalyst, 5 mL acetonitrile, 75 °C, and 9 h.

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