溶剂热法合成UiO-66金属有机框架限域的钴取代磷钼酸及其催化烯烃环氧化性能

doi:10.1016/S1872-2067(20)63665-8

摘要/Abstract

摘要：

金属有机框架材料是一类新型晶体孔性材料, 在气体储存、物质分离、非线性光学及催化等领域中具有潜在应用价值. 其中, 基于锆氧簇和有机配体构筑的锆基金属有机框架材料(ZrMOFs)因其具有更高的结构稳定性而备受关注. 研究表明, 将多金属氧酸盐(POM)负载在ZrMOFs载体上能够获得一类新型复合材料催化剂. 这类材料具有可调控的酸性和氧化还原性, 已在一些固体酸催化及选择氧化（包括烯烃环氧化）等反应中表现出优异的催化性能.
多金属氧酸盐通常可以通过简单的浸渍法引入到ZrMOFs载体上, 但这种方法制备的催化剂普遍存在活性组分分散不均匀且易于在液相催化反应过程中发生活性组分流失的问题. 因此, 当前的研究重点主要集中在如何通过简单有效的制备方法获得结构更加稳定、性能更加优异的复合材料催化剂. 近期, 国内外多个研究小组分别报道了采用溶剂热法能够一步合成出POM@ZrMOFs复合材料, 这类材料的主要特点是POM团簇能够均匀的分散在ZrMOFs孔道中, 从而使其在氧化脱硫及烯烃选择氧化等反应中表现出更高的稳定性. 考虑到POMs及ZrMOFs种类和结构的多样性, 可以预期这类复合材料的合成及催化性能研究仍有很大的发展空间.
本文采用溶剂热法将磷钼酸(PMo₁₂)及钴取代磷钼酸(PMo₁₁Co)限域在一类ZrMOFs材料(UiO-66)的孔道中, 得到了两种复合材料催化剂, 分别记为PMo₁₂@UiO-66和PMo₁₁Co@UiO-66. 通过以叔丁基过氧化氢(t-BuOOH)为氧化剂烯烃环氧化反应考察了其催化性能. 相较于PMo₁₂@UiO-66, 含有钴取代磷钼酸的PMo₁₁Co@UiO-66杂化材料表现出了更高的催化活性和稳定性. 催化剂经简单的过滤和洗涤后即可循环使用多次, 且催化性能基本保持不变. 值得一提的是, PMo₁₁Co@UiO-66对多种类型烯烃的环氧化反应均表现出较高的催化活性和环氧选择性. 例如, 在加入自由基抑制剂对二苯酚后, 柠檬烯选择性氧化为柠檬烯-1,2-环氧化物的选择性可以达到91%, 性能明显优于文献中报道的其它类型催化剂. 此外, 溶剂种类对PMo₁₁Co@UiO-66的催化活性有着显著的影响, 在极性相对较强的乙醇、乙腈等溶剂中, 催化剂的活性较低; 在极性较弱的甲苯、氯仿, 四氯化碳等溶剂中, 催化剂的活性则相对较高. 溶剂极性的差异会影响反应物分子与催化剂活性中心的接触情况, 继而对催化剂的活性产生较大影响.
采用X射线衍射、氮吸附-脱附、X射线光电子能谱、傅立叶变换红外光谱(FT-IR)等手段对催化反应前后的PMo₁₁Co@UiO-66催化剂进行了表征. 结果表明, 在溶剂热法合成的杂化材料催化剂中, 引入的POM团簇能够均匀的分散在UiO-66框架材料的孔道和笼中; 催化剂反应前后的组成与结构没有发生明显的变化. 结合相关文献报道的结果, 可以认为杂原子Co的引入能够产生类似于Co-O-Mo的新的活性中心, 从而使PMo₁₁Co@UiO-66表现出更高的催化活性. 催化剂的高稳定性应主要归因于UiO-66框架对PMo₁₁Co团簇的空间限域作用. 这种空间限域作用能够使PMo₁₁Co团簇被封装在UiO-66的八面体笼中, 且二者之间还存在着较强的金属-载体间相互作用. 在后续的工作中, 我们还将继续深入研究PMo₁₁Co@UiO-66催化剂的活性中心性质及其对分子氧的活化能力, 加深对催化作用机制等问题的理解, 进一步扩大这类复合材料催化剂的应用范围.

关键词: 多金属氧酸盐, 金属有机框架, 烯烃, 环氧化, 溶剂热合成

Abstract:

Hybrid composites of phosphomolybdic acid@UiO-66 (PMo₁₂@UiO-66) and Co-substituted phosphomolybdic acid@UiO-66 (PMo₁₁Co@UiO-66) were synthesized using the direct solvothermal method. A variety of characterization results demonstrated that phosphomolybdic acid (PMo₁₂) or Co-substituted phosphomolybdate acid (PMo₁₁Co) clusters are uniformly dispersed in the cages of Zr-based metal-organic UiO-66 frameworks. The catalytic properties of these hybrid composites were investigated by applying the epoxidation of olefins with tert-butyl hydroperoxide as the oxidant. Compared to PMo₁₂@UiO-66, PMo₁₁Co@UiO-66 showed a much higher catalytic activity and was simply recovered by filtration and reused for at least ten runs without significant loss of catalytic activity. Particularly, PMo₁₁Co@UiO-66 can efficiently convert cyclic olefins like limonenes to epoxides, and its selectivity to 1,2-limonene oxide reached 91% in the presence of a radical inhibitor such as hydroquinone. The excellent catalytic activity and stability of the hybrid composite PMo11Co@UiO-66 are mainly attributed to the uniform distribution of highly active PMo11Co units within the smaller cages of UiO-66, to the suitable surface polarity of the hybrid composite for facilitating the access of reagents and solvent, and to the strong interface-interactions between the polyoxometalate and the UiO-66 framework.

Key words: Polyoxometalate, Metal-organic frameworks, Olefins, Epoxidation, Solvothermal synthesis

扈殿文, 宋晓静, 吴淑杰, 杨晓彤, 张浩, 常鑫瑜, 贾明君. 溶剂热法合成UiO-66金属有机框架限域的钴取代磷钼酸及其催化烯烃环氧化性能[J]. 催化学报, 2021, 42(2): 356-366.

Dianwen Hu, Xiaojing Song, Shujie Wu, Xiaotong Yang, Hao Zhang, Xinyu Chang, Mingjun Jia. Solvothermal synthesis of Co-substituted phosphomolybdate acid encapsulated in the UiO-66 framework for catalytic application in olefin epoxidation[J]. Chinese Journal of Catalysis, 2021, 42(2): 356-366.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63665-8

https://www.cjcatal.com/CN/Y2021/V42/I2/356

图/表 16

Table 1 Textural parameters derived from N2 adsorption-desorption profiles as well as element compositions determined by ICP-OES analyses of various materials.

Sample	BET surface area (m²·g^-1)	Pore volume (cm³·g^-1)	Pore diameter (nm)	POM loading (mmol·g^-1/wt%)	Mo loading (mmol·g^-1/wt%)	Co loading (mmol·g^-1/wt%)
UiO-66	1202	0.58	1.9	—	—	—
PMo₁₂@UiO-66	994	0.53	2.1	(0.040/7.3)	(0.480/4.6)	—
PMo₁₁Co@UiO-66	991	0.51	2.0	(0.038/6.7)	(0.418/4.0)	(0.038 /0.2)
PMo₁₁Co/UiO-66-imp	956	0.47	1.9	(0.037/6.6)	(0.407/3.9)	(0.037 / 0.2)

Fig. 1. XRD patterns of simulated UiO-66, UiO-66, and POM@UiO-66 composites.

Fig. 2. SEM images of UiO-66 (a), PMo12@UiO-66 (b), and PMo11Co@UiO-66 (c); (d,e) TEM images of PMo11Co@UiO-66; (f) HAADF-STEM image of PMo11Co@UiO-66; (g-i) EDS mapping images of PMo11Co@UiO-66.

Fig. 3. TG curves of UiO-66, PMo12@UiO-66, and PMo11Co@UiO-66.

Fig. 4. (A) N2 adsorption-desorption isotherms of UiO-66, PMo12@UiO-66, and PMo11Co@UiO-66 composites; (B) Pore size distribution curves of UiO-66, PMo12@UiO-66, and PMo11Co@UiO-66 composites.

Fig. 5. FT-IR spectra of PMo12, PMo11Co, UiO-66, and POM@UiO-66 composites.

Fig. 6. (A) DR-UV-vis spectra of PMo12 and PMo11Co; (B) DR-UV-vis spectra of UiO-66 and POM@UiO-66 composites.

Fig. 7. (A) XPS profiles for the binding energies of Mo 3d in PMo12, PMo11Co, PMo11Co@UiO-66, and reused PMo11Co@UiO-66; (B) XPS profiles for the binding energies of Co 2p in PMo11Co, PMo11Co@UiO-66, and reused PMo11Co@UiO-66.

Table 2 Cyclooctene epoxidation performance of various catalyst samples a.

Entry	Catalyst	Amount of catalyst (mg)	Time (h)	Conversion (%)	TOF^b(h^-1)	Related work
1	Blank	—	6	3	—	This work
2	UiO-66	10	6	3	—	This work
3	PMo₁₂@UiO-66	10	6	32	11	This work
4	PMo₁₁Co@UiO-66	10	6	52	19 ^c	This work
5	PMo₁₁Co/UiO-66-imp	10	6	40	15 ^c	This work
6	PMo₁₂@COF-300 ^f	10	3	63	44	[40]
7	Mo(CO)₃-L@UiO-66 ^d	100	4.5	98	19	[46]
8	PMo₁₂@meso-organosilicates ^e	100	6	58	4	[47]

Fig. 8. Leaching (A) and recycling (B) experiments of PMo11Co@UiO-66. Reaction conditions: cyclooctene 5.0 mmol, t-BuOOH 5.0 mmol, PMo11Co@UiO-66 50 mg, solvent 15 ml, 334 K, 6 h. All epoxide selectivity was greater than 99%.

Fig. 9. Solvent effect on cyclooctene epoxidation. Reaction conditions: cyclooctene 1.0 mmol, t-BuOOH 1.0 mmol, PMo11Co@UiO-66 10 mg, solvent 3 ml, 334 K, 6 h. Selectivity for the epoxide is greater than 99%.

Table 3 Epoxidation of olefins catalyzed by PMo11Co@UiO-66 a.

Entry	Conversion^c (%)	Selectivity^c(%)	TOF (h^-1)
1^b	55	69^d	10
2	68	>99	12
3	61	71^d	11
4	63	74^d	12
5	16	>99	3
6	12	>99	2
7	42	69^d	8

Fig. 10. Conversion and selectivity during selective limonene oxidation. Reaction conditions: limonene 10 mmol, t-BuOOH 20 mmol, catalyst 100 mg, chloroform 30 mL, reaction temperature 334 K.

Fig. 11. Scheme 1. Typical synthesis of POM@UiO-66 composites.

Fig. 12. Scheme 2. Main products of selective limonene oxidation.

Fig. 13. Scheme 3. Proposed oxygen activation mechanism of t-BuOOH.

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