核壳型MOFs@离子液体复合材料的制备及其常压下催化CO<sub>2</sub>环加成反应性能探究

胡凤群; 邱明月; 易群; 张鼎; 李向远; 李剑川; 史利娟; 段小川

doi:10.19906/j.cnki.JFCT.2023028

核壳型MOFs@离子液体复合材料的制备及其常压下催化CO₂环加成反应性能探究

doi: 10.19906/j.cnki.JFCT.2023028

胡凤群^1,,
邱明月^2,,
易群^{2, 3,},
张鼎^2,,
李向远^4,,
李剑川^4,,
史利娟^{2, 4, ,},
段小川^1, ,

1.
太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 山西太原 030024
2.
武汉工程大学化工与制药学院, 湖北武汉 430205
3.
山西浙大新材料与化工研究院, 山西太原 030000
4.
天脊煤化工集团有限公司, 山西长治 046000

基金项目: 国家自然科学基金面上基金（22272125），榆林学院中国科学院洁净能源创新研究院联合基金（YLU-DNL Fund 2021021），武汉市科技局知识创新专项基础研究项目（2022020801010354）和山西浙大新材料与化工研究院项目（2022SXTD015）资助

详细信息

通讯作者:
Tel: 15364834561, 15959459816, E-mail: shilijuanwit@sina.com

duanxiaochuan@tyut.edu.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2023-01-17
- 修回日期: 2023-03-29
- 录用日期: 2023-04-03
- 网络出版日期: 2023-04-13
- 刊出日期: 2023-11-13

Construction of core-shell MOFs@ionic liquid materials and their performance for CO₂ cycloaddition reaction under atmospheric pressure

HU Feng-qun^1
,,
QIU Ming-yue^2
,,
YI Qun^{2, 3
,},
ZHANG Ding^2
,,
LI Xiang-yuan^4
,,
LI Jian-chuan^4
,,
SHI Li-juan^{2, 4
, ,},
DUAN Xiao-chuan^{1
, ,}

1.
State Key Laboratory of Clean and Efficient Utilization of Coal-based Energy, Taiyuan university of technology, Taiyuan 030021, China
2.
School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China
3.
Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering
4.
Shanxi Tianji Coal Chemical Industry Group Co.Ltd, Changzhi 046000, China

Funds: The project was supported by the National Natural Science Foundation of China (22272125), the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2021021), the Knowledge Innovation Program of Wuhan -Basic Research (2022020801010354) and Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2022SXTD015)

摘要

摘要: 通过双氨基功能化离子液体与对苯二甲醛原位共价组装得到柔性聚合物（DP），并采用后合成修饰法将DP包覆于金属有机框架材料MIL-101（Cr）表面，构筑了一种核-壳型复合材料（MIL-101@DP）用于催化CO₂和环氧氯丙烷（ECH）环加成反应。MIL-101@DP保留了MIL-101（Cr）高比表面积和高孔隙率的优点，并兼具亲核位点Cl⁻与Lewis酸性位点Cr^{3 +}。在Lewis酸碱位点协同作用下，MIL-101@DP可在常压、80 ℃、24 h且无助催化剂的条件下高效催化转化CO₂和ECH反应（ECH转化率可达99%），且在循环使用四次后活性未出现明显下降。
- MOFs@ILs复合材料 /
- 核-壳结构 /
- CO₂ /
- 环加成反应 /
- 环氧氯丙烷
Abstract: A flexible polymer (DP) was prepared by in-situ covalent assembly of dual-amino-functionalized ionic liquids and terephthalaldehyde. A core-shell composite (MIL-101@DP) was constructed by coating DP on the surface of metal-organic frame material MIL-101 (Cr) by post-synthesis modification, and was applied to catalyze the cycloaddition reaction of CO₂ and epichlorohydrin (ECH). MIL-101@DP retains the advantage of high specific surface area and high porosity of MIL-101 (Cr), and combines the nucleophilic site Cl⁻ and Lewis acidic site Cr^{3 +}. Under the synergistic interaction of Lewis acid sites and Lewis base sites, MIL-101@DP could efficiently catalyze activity the conversion of CO₂ and ECH reaction (ECH conversion rate can reach 99%) at atmospheric pressure, 80 ℃, 24 h and without cocatalyst. The activity did not decrease significantly after four cycles.
- MOFs@ILs composites /
- core-shell structure /
- CO₂ /
- cycloaddition reaction /
- epichlorohydrin

HTML全文

FIG. 2766. FIG. 2766.

FIG. 2766. FIG. 2766.

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图 1 1.4-丁基二咪唑反应方程式

Figure 1 Reaction formula for the synthesis of 1,4-bis (imidazol-1-yl) butane

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图 2 离子液体DAIL的反应方程式

Figure 2 Reaction formula for the synthesis of inion liquid DAIL

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图 3 聚合物DP反应方程式

Figure 3 Reaction formula for the synthesis of polymer DP

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图 4 ECH和CO₂环加成反应

Figure 4 The cycloaddition of ECH and CO₂

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图 5 （a）TPA、DAIL、DP的红外光谱谱图；（b）MIL-101、MIL-101-DAIL、MIL-101@DP-X的红外光谱谱图

Figure 5 (a) FT-IR spectra of TPA, DAIL and DP; (b) FT-IR spectra of MIL-101, MIL-101-DAIL and MIL-101@DP-X

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图 6 MIL-101、MIL-101-DAIL、MIL-101@DP-X的XRD谱图

Figure 6 Powder XRD patterns of MIL-101, MIL-101-DAIL and MIL-101@DP-X

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图 7 N₂吸附-脱附等温曲线（a）和孔径分布（b）

Figure 7 (a) N₂ adsorption-desorption isotherms and (b) pore diameter distributions

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图 8 （a）、（b）MIL-101的SEM照片；（c）、（d）MIL-101@DP-2的SEM照片

Figure 8 SEM images spectra of (a), (b) MIL-101, and (c), (d) MIL-101@DP-2

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图 9 MIL-101、MIL-101-DAIL、MIL-101@DP-X的DTG曲线（a）和TGA曲线（b）

Figure 9 DTG (a) and TGA (b) curves of MIL-101, MIL-101-DAIL and MIL-101@DP-X

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图 10 MIL-101、MIL-101-DAIL、MIL-101@DP-X在0.1 MPa、50 ℃、24 h下的催化性能

Figure 10 Catalytic performance of MIL-101, MIL-101-DAIL and MIL-101@DP-X at 0.1 MPa, 50 ℃ for 24 h

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图 11 MIL-101@DP-2在0.1 MPa、24 h、不同温度下的催化性能

Figure 11 Catalytic performance of MIL-101@DP-2 at 0.1 MPa, 24 h and different temperatures

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图 12 MIL-101@DP-2在0.1 MPa、80 ℃、24 h下的循环使用性能

Figure 12 Cyclic performance of the MIL-101@DP-2 at 0.1 MPa, 80 ℃ for 24 h

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图 13 MIL-101@DP-2新鲜和回收后的（a）N₂吸附-脱附等温曲线，（b）孔径分布，（c）FT-IR谱图，（d）XRD 谱图

Figure 13 (a) N₂ adsorption-desorption isotherms, (b) pore diameter distributions, (c) FT-IR spectra and (d) XRD patterns of fresh and recycled MIL-101@DP-2

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图 14 MIL-101@DP催化机理示意图

Figure 14 Proposed catalytic reaction mechanism of MIL-101@DP

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表 1 MIL-101、MIL-101-DAIL、MIL-101@DP-X的比表面积和孔容

Table 1 Specific surface areas and pore volumes of MIL-101, MIL-101-DAIL and MIL-101@DP-X

S_BET /(m²·g⁻¹) v_total /(cm³·g⁻¹)

MIL-101 1766 1.07
MIL-101-DAIL 968 0.67
MIL-101@DP-1 1618 1.03
MIL-101@DP-2 1652 1.02

下载: 导出CSV

表 2 MIL-101@DP-2催化CO₂与各种环氧化合物合成碳酸盐

Table 2 Synthetic carbonates from various epoxides catalyzed by MIL-101@DP-2

Entry Substrate Product Temperature /℃ p /MPa Conversion /%

1 80 0.1 99
2 80 0.1 99
3 80 0.1 59
4 80 0.1 29

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核壳型MOFs@离子液体复合材料的制备及其常压下催化CO₂环加成反应性能探究

doi: 10.19906/j.cnki.JFCT.2023028

通讯作者:
Tel: 15364834561, 15959459816, E-mail: shilijuanwit@sina.com

duanxiaochuan@tyut.edu.cn

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Construction of core-shell MOFs@ionic liquid materials and their performance for CO₂ cycloaddition reaction under atmospheric pressure

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2023年《燃料化学学报（中英文）》评优结果公布！

	S_BET /(m²·g⁻¹)	v_total /(cm³·g⁻¹)
MIL-101	1766	1.07
MIL-101-DAIL	968	0.67
MIL-101@DP-1	1618	1.03
MIL-101@DP-2	1652	1.02

Entry	Substrate	Product	Temperature /℃	p /MPa	Conversion /%
1			80	0.1	99
2			80	0.1	99
3			80	0.1	59
4			80	0.1	29

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核壳型MOFs@离子液体复合材料的制备及其常压下催化CO2环加成反应性能探究

doi: 10.19906/j.cnki.JFCT.2023028

通讯作者: Tel: 15364834561, 15959459816, E-mail: shilijuanwit@sina.com duanxiaochuan@tyut.edu.cn

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Construction of core-shell MOFs@ionic liquid materials and their performance for CO2 cycloaddition reaction under atmospheric pressure

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出版历程

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2023年《燃料化学学报（中英文）》评优结果公布！

核壳型MOFs@离子液体复合材料的制备及其常压下催化CO₂环加成反应性能探究

通讯作者:
Tel: 15364834561, 15959459816, E-mail: shilijuanwit@sina.com

duanxiaochuan@tyut.edu.cn

Construction of core-shell MOFs@ionic liquid materials and their performance for CO₂ cycloaddition reaction under atmospheric pressure