功能化氧化石墨烯催化CO<sub>2</sub>的化学固定

卢金凯; 张梦; 李斌; 董丽辉; 范闽光

doi:10.6054/j.jscnun.2021041

功能化氧化石墨烯催化CO₂的化学固定

doi: 10.6054/j.jscnun.2021041

广西大学化学化工学院//广西石化资源加工及过程强化技术重点实验室，南宁 530004

基金项目:

国家自然科学基金项目 21968002

广西石化资源加工及过程强化技术重点实验室项目 2019k006

详细信息

通讯作者:
范闽光，Email: fanmg@gxu.edu.cn

中图分类号: O643.32
计量
- 文章访问数: 425
- HTML全文浏览量: 194
- PDF下载量: 31
- 被引次数: 0
出版历程
- 收稿日期: 2021-03-15
- 网络出版日期: 2021-07-06
- 刊出日期: 2021-06-25

Chemical Fixation of CO₂ Catalyzed by Functionalized Graphene Oxide

School of Chemistry and Chemical Engineering, Guangxi University//Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Nanning 530004, China

摘要

摘要: 通过一锅法将氨基官能化的咪唑离子液体嫁接在氧化石墨烯(GO)和硅铝酸盐中孔分子筛(SBA-15)上，用来催化合成环状碳酸酯. 通过傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、热重分析(TGA)和元素分析(EA)对催化剂的结构、热稳定性以及氨基官能化咪唑离子液体的嫁接量进行了研究. 在环加成反应过程中，GO-NH₂的活性高于SBA-15-NH₂. 最佳条件: 催化剂用量0.15 g、反应温度130 ℃、CO₂压力1.5 MPa和反应时间5 h，碳酸丙烯酯的产率达到96.46%. 此外，催化剂具有可回收性并可以连续5次重复使用.
- 环状碳酸酯 /
- 氧化石墨烯 /
- 离子液体 /
- 非均相催化 /
- 环氧化物 /
- SBA-15
Abstract: The amino-functionalized imidazole ionic liquid (IL) was supported on graphene oxide (GO) and Santa Barbara Amorphous mesoporous molecular sieves (SBA-15) through the facile and simplified one-pot grafting approach to catalyze the synthesis of cyclic carbonates. The structure and thermal stability of the catalyst and the loading of the amino-functionalized imidazole IL were studied in detail with Fourier transforn infrared spectroscopy(FT-IR), scanning electron microscope(SEM), thermogravimetric analysis(TGA) and elemental analysis(EA). During the cycloaddition reaction, GO-NH₂ exhibited higher activity than SBA-15-NH₂. The optimum condition was 0.15 g catalyst, 130 ℃, 1.5 MPa CO₂ pressure and 5 h of reaction time, and the yield of propylene carbonate reached 96.46%. Furthermore, the supported catalyst exhibited promising recyclability and reusability for five consecutive reuses.
- cyclic carbonates /
- graphene oxide /
- ionic liquid /
- heterogeneous catalysis /
- epoxide /
- SBA-15

HTML全文

图 1 SBA-15-NH₂和GO-NH₂的合成路线

Figure 1. The route of SBA-15-NH₂ and GO-NH₂ synthesis

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图 2 环状碳酸酯的合成

Figure 2. The synthesis of cyclic carbonates

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图 3 不同材料的FT-IR光谱

Figure 3. The FT-IR spectra of different materials

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图 4 不同材料的SEM图

Figure 4. The SEM images of different materials

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图 5 GO和GO-NH₂的TGA曲线

Figure 5. The TGA curves of GO and GO-NH₂

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图 6 SBA-15和SBA-15-NH₂的TGA曲线

Figure 6. The TGA curves of SBA-15 and SBA-15-NH₂

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图 7 各种参数对GO-NH₂催化条件下PC产率和选择性的影响

Figure 7. The effects of various parameters on the PC yield and selectivity with GO-NH₂ as the catalyst

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图 9 GO-NH₂催化剂的循环性能

Figure 9. The recycling performance of the GO-NH₂ catalyst

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表 1 各种样品的元素分析结果

Table 1. The elemental analysis results of various samples

编号	样品	w(C)/%	w(N)/%	嫁接量/(mmol·g^-1)	嫁接率/%
1	GO	48.42	—	—	—
2	GO-NH₂	26.04	7.24	1.730	46.78
3	GO-NH₂(循环5次后)	28.63	7.23	1.720	46.77
4	SBA-15	—	—	—	—
5	SBA-15-NH₂	12.05	8.29	1.975	53.42
6	SBA-15-NH₂(循环5次后)	12.01	8.27	1.974	53.41

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表 2 各种催化剂对CO₂环加成生成PC的性能

Table 2. The performance of various catalysts for the cycloaddition of CO₂ to form PC

实验序号	催化剂	PC产率/%	PC选择性/%
1	无	痕量	—
2	N-methylimidazole	< 3	100
3	2-Bromoethylamine	19.06	98
4	GO	15.05	98
5	GO-NH₂	96.46	99
6	SBA-15	8.51	98
7	SBA-15-NH₂	90.47	99
注：PO为34.5 mmol，催化剂质量为0.15 g，压力为1.5 MPa，温度为130 ℃，反应时间为5 h.

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表 3 GO-NH₂与各种同类催化剂的催化活性比较

Table 3. The performance of various catalysts for CO₂ and PO cycloaddition reaction

序号	催化剂	温度/℃	压力/MPa	时间/h	产率/%	参考文献
1	GO-HEIMBr	140	2	4	99	[24]
2	EG/HEBIMBr	120	2	4	96	[21]
3	GO/[BMIM]Br	80	1	6	99	[22]
4	PS-HEIMBr	120	2.5	4	98	[23]
5	GO-[SMIM]I	140	2	4	93	[24]
6	GO-NH₂	130	1.5	5	96.4	本文

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