分子氧环氧化烯烃多相催化剂PCuMo<sub>11</sub>/富氮类共价有机骨架材料的制备及应用

高文秀; 吕杰琼; 邢树宇; 谢晖; 高永平; 娄大伟

doi:10.13801/j.cnki.fhclxb.20211108.003

分子氧环氧化烯烃多相催化剂PCuMo₁₁/富氮类共价有机骨架材料的制备及应用

doi: 10.13801/j.cnki.fhclxb.20211108.003

吉林化工学院　化学与制药工程学院，吉林 132022

基金项目: 吉林省科技发展计划项目(2020122373JC)；吉林省产业技术研究与开发项目(No.2020C028-1)；吉林省教育厅科研规划项目(JJKH20200240KJ)；吉林市科技局杰出青年人才培养项目(201831757)；吉林省精细化工重点实验室(20140622023JC)

详细信息

通讯作者:
高文秀，博士，副教授，硕士生导师，研究方向为多相催化　E-mail：gaowenxiu-0922@163.com

中图分类号: O643.36
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出版历程
- 收稿日期: 2021-09-09
- 修回日期: 2021-10-16
- 录用日期: 2021-10-31
- 网络出版日期: 2021-11-09
- 刊出日期: 2022-08-22

Preparation and application of heterogeneous catalyst PCuMo₁₁/ nitrogen rich covalent organic framework material for olefin epoxidation with molecular oxygen oxidant

School of Chemical and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022, China

摘要

摘要: 环氧化合物是一类重要的有机合成中间体和化工原料，主要通过烯烃环氧化反应获得。制备在分子氧环境下高效、稳定、可重复使用的烯烃环氧化反应新型催化剂是一项十分有意义的工作。以富氮类共价有机骨架材料(PC)为载体，多金属氧酸盐PCuMo₁₁为活性物质，制备了复合材料PCuMo₁₁/PC。通过FT-IR、N₂吸附脱附、XPS、TEM及EDS等测试对材料进行了表征，并将PCuMo₁₁/PC应用于多相催化分子氧气氛下的烯烃(苯乙烯、1-辛烯、环辛烯和环十二烯)环氧化反应中，取得了较高的催化活性和选择性，循环使用5次以上催化活性没有明显下降。实验结果显示，二维层状富氮类共价有机骨架材料的高表面积及骨架中丰富的氮元素含量，有利于均匀地分散催化活性物质多金属氧酸盐，并与其建立相对稳定的化学链接，提高复合材料的催化活性及稳定性。
- 共价有机骨架材料(COF) /
- 多金属氧酸盐(POM) /
- 复合材料 /
- 催化剂 /
- 烯烃 /
- 环氧化
Abstract: Epoxide is an important organic synthesis intermediate and chemical raw material that is mainly prepared from the olefin epoxidation. It is a very interesting work to prepare efficient catalysts with stability and recyclability for aerobic olefins epoxidation. Composite PCuMo₁₁/PC was prepared by using the nitrogen rich covalent organic framework material (PC) as support and the polyoxometalate PCuMo₁₁ as active substance. The materials were characterized by FT-IR, N₂ adsorption and desorption, XPS, TEM and EDS. The application of PCuMo₁₁/PC for heterogeneous catalytic epoxidation of olefins (styrene, 1-octene, cyclooctene, cyclododecene) with molecular oxygen oxidant has obtained high catalytic activity and selectivity. There is no significant decrease in catalytic activity after recycling over five times. The experimental results show that large surface area and rich nitrogen content in the skeleton of the two-dimensional layered nitrogen rich covalent organic framework material are benefit to disperse the catalytic active substance polyoxometalate uniformly and establish a relatively stable chemical link, so as to improve the catalytic activity and stability of the composite.
- covalent organic framework (COF) /
- polyoxometallate (POM) /
- composites /
- catalyst /
- olefins /
- epoxidation

HTML全文

图 1 PMo₁₂、富氮类共价有机骨架材料(PC)、PCuMo₁₁和PCuMo₁₁/PC的FTIR图谱

Figure 1. FTIR spectra of PMo₁₂, nitrogen rich covalent organic framework material (PC), PCuMo₁₁ and PCuMo₁₁/PC

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图 2 PC和PCuMo₁₁/PC的N₂吸附-脱附等温线(a)和孔径分布曲线(b)

Figure 2. N₂ adsorption-desorption isotherm (a) and pore size distribution curves (b) of PC and PCuMo₁₁/PC

STP—Standard temperature and pressure

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图 3 PCuMo₁₁/PC (a)、Mo3d (b)、Cu2p (c) 和N1s (d)的XPS能谱

Figure 3. XPS spectra of PCuMo₁₁/PC composite (a), Mo3d (b), Cu2p (c) , N1s (d)

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图 4 PCuMo₁₁/PC的TEM图像和EDS面扫图像

Figure 4. TEM and EDS images of PCuMo₁₁/PC

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图 5 PCuMo₁₁/PC催化苯乙烯 (a)、环辛烯 (b)、环十二烯 (c) 和1-辛烯 (d) 环氧化反应的循环实验

Figure 5. Recycling experiments of styrene (a), cyclooctene (b), cyclododecene (c) and 1-octene (d) epoxidation over PCuMo₁₁/PC

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表 1 PC和PCuMo₁₁/PC的物理性质

Table 1. Physical performance of PC and PCuMo₁₁/PC

Sample	S_BET /(m²·g⁻¹)	Mode pore size/nm	Pore volume/ (cm³·g⁻¹)
PC	216	1.30	0.6
PCuMo₁₁/PC	60	1.43	0.2
Notes: S_BET—Specific surface area.

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表 2 PCuMo₁₁/PC催化不同烯烃环氧化反应的催化性能

Table 2. Catalytic performance of PCuMo₁₁/PC in different olefins epoxidation

Substrate	Time/h	Conversion/%	Epoxide selectivity/%	Yield/%
Styrene	1	98	84	82
Cyclooctene	1	98	≥99	98
Cyclododecene	1	95	≥99	95
1-octene	6	99	≥99	99
Note: Substrate olefin 2 mmol, catalyst PCuMo₁₁/PC 20 mg, solvent CH₃CN 10 mL, IBA 6 mmol, O₂ 10 mL/min, temperature 60℃, unless otherwise mentioned.

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表 3 PCuMo₁₁/PC与同类催化剂催化烯烃环氧化反应性能比较

Table 3. Catalytic performance comparison of PCuMo₁₁/PC with other reported catalysts for olefins epoxidation

Entry	Catalyst	Substrate	Oxidant	Time /h	Conversion /%	Epoxide selectivity/%	TOF/(10^{− 3} mol·g^{− 1}·h^{− 1})	Ref.
1	PCuMo₁₁/PC	Styrene	O₂	1	98	84	98	This work
2	PMo₁₁Co/SBA	Styrene	Air	1	89	7	89	[25]
3	POSS-OIM₈-PW	Styrene	H₂O₂	6	72	66	12	[26]
4	CoPMA/POP-II	Styrene	H₂O₂	9	67	14	8	[27]
5	PCuMo₁₁/PC	Cyclooctene	O₂	1	98	≥ 99	98	This work
6	POSS-OIM₈-PW	Cyclooctene	H₂O₂	2	100	100	50	[26]
7	PMo₁₁Co/SBA	Cyclooctene	Air	3	98	≥ 99	33	[25]
8	PMA@COF-300	Cyclooctene	TBHP	3	91	≥ 99	30	[18]
9	Fe/PMA@CIN− 1	Cyclooctene	H₂O₂	9	88	≥ 99	10	[28]
10	CoPMA/POP-II	Cyclooctene	H₂O₂	9	80	≥ 99	9	[27]
11	PCuMo₁₁/PC	Cyclododecene	O₂	1	95	≥ 99	95	This work
12	PMA@COF-300	Cyclododecene	TBHP	3	34	≥ 99	11	[18]
13	Fe/PMA@CIN− 1	Cyclododecene	H₂O₂	9	58	≥ 99	6	[28]
14	PCuMo₁₁/PC	1-octene	O₂	6	99	≥ 99	17	This work
15	POSS-OIM₈-PW	1-octene	H₂O₂	6	51	99	9	[26]
16	PMA@COF-300	1-octene	TBHP	9	77	≥ 99	9	[18]
Notes: TBHP—Tert-butyl hydroperoxide; SBA—SBA-15 (Santa barbara amorphous-15); POSS-OIM₈-PW—POSS-derived mesoporous ionic copolymer-polyoxometalate (POSS—Polyhedral oligomeric silsesquioxanes, OIM₈—[3-Octyl-1-vinylimidazolium]Br, PW—Phospho-tungstic acid); CoPMA/POP-II—Triphenylamine-based porous organic polymers supporting cobalt phosphomolybdate (CoPMA—Cobalt phosphomolybdate, POP-II—Triphenylamine-based porous organic polymers); PMA@COF-300—Heteropolyacid-based hybrid composite (PMA—Phosphomolybdic acid, COF-300—Covalent organic framework material); CIN—Covalent imine network; Turnover frequency $\left(\mathrm{T}\mathrm{O}\mathrm{F}\right)\;\;=\dfrac{\mathrm{M}\mathrm{o}\mathrm{l}\mathrm{e}\;\;\mathrm{o}\mathrm{f}\;\;\mathrm{c}\mathrm{o}\mathrm{n}\mathrm{v}\mathrm{e}\mathrm{r}\mathrm{t}\mathrm{e}\mathrm{d}\;\;\mathrm{s}\mathrm{u}\mathrm{b}\mathrm{s}\mathrm{t}\mathrm{r}\mathrm{a}\mathrm{t}\mathrm{e}}{\mathrm{C}\mathrm{a}\mathrm{t}\mathrm{a}\mathrm{l}\mathrm{y}\mathrm{s}\mathrm{t}\left(\mathrm{g}\right)\times\mathrm{R}\mathrm{e}\mathrm{a}\mathrm{c}\mathrm{t}\mathrm{i}\mathrm{o}\mathrm{n}\;\;\mathrm{t}\mathrm{i}\mathrm{m}\mathrm{e}\left(\mathrm{h}\right)} $

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