One-pot construction of ionic liquid-functionalized MOF material as the catalyst for CO2 cycloaddition under atmospheric pressure
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摘要: 采用原位组装法将羧基离子液体1-丙酸-3-甲基咪唑氯（CFIL）一步固载到一种金属有机框架（MOF）材料NH2-MIL-101上，制备了具有多重活性位点的非均相催化剂NH2-FMOF-CFIL，对其在CO2和环氧氯丙烷的（ECH）环加成反应中的催化性能进行了研究。傅里叶变换红外光谱（FT-IR）和元素分析结果证实离子液体CFIL引入到MOF材料中，粉末X射线衍射（PXRD）、扫描电子显微镜（SEM）和N2吸脱附结果表明离子液体的引入不会破坏NH2-MIL-101的MOF晶体结构或堵塞孔道，但能诱导产生介孔。催化反应表征结果显示，离子液体CFIL结构中咪唑N作为Lewis碱性位点活化CO2，Cl−作为亲核试剂促进环氧氯丙烷开环，并与MOF材料NH2-MIL-101上的Cr3+和氨基产生协同作用，诱导在温和条件（0.1 MPa CO2、25–70 ℃、无溶剂和助剂）下，高效催化转化CO2生成氯丙烯碳酸酯，反应24 h氯丙烯碳酸酯收率可达99%，且循环使用5次后，催化剂晶体结构和高活性仍能保持稳定。Abstract: Carboxylic ionic liquid 1-propionic acid-3-methylimidazolium chloride (CFIL) was immobilized in a metal-organic framework (MOF) material NH2-MIL-101 in one-pot by the in-situ assembly method; as a heterogeneous catalyst with multiple active sites, the catalytic performance of NH2-FMOF-CFIL in the cycloaddition of CO2 with epichlorohydrin (ECH) to synthesize chloropropylene carbonate (CPC) was investigated. The immobilized of CFIL in NH2-MIL-101 was proved by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis, while the powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and N2 adsorption-desorption measurements demonstrated that CFIL neither damages the crystal structure nor blocks the pore of NH2-MIL-101, but induce the formation of mesopores. The catalytic reaction results reveal that there is a catalytic synergy between imidazole N and Cl− on CFIL and Cr3+ and amino group on MOF, which endow the NH2-FMOF-CFIL composite excellent catalytic performance in the cycloaddition of CO2 with ECH; under mild conditions, viz., 0.1 MPa CO2, 25–70 ℃ and without using any solvent and cocatalyst, the CPC yield reaches 99% after reaction for 24 h. Moreover, the crystal structure and high activity of the NH2-FMOF-CFIL catalyst are well preserved even after reuse for 5 cycles.
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Key words:
- ionic liquids /
- heterogeneous catalyst /
- CO2 /
- chloropropylene carbonate /
- mild conditions
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图 3 NH2-FMOF-CFIL的反应方程式
Figure 3 Reaction formula for the synthesis of NH2-FMOF-CFIL composite
图 4 CFIL、NH2-MIL-101和NH2-FMOF-CFIL的红外光谱谱图
Figure 4 FT-IR spectra of CFIL, NH2-MIL-101 and NH2-FMOF-CFIL
图 5 NH2-MIL-101和NH2-FMOF-CFIL的PXRD谱图
Figure 5 PXRD patterns of NH2-MIL-101 and NH2-FMOF-CFIL
图 6 (a) NH2-MIL-101 SEM照片(b) NH2-FMOF-CFIL SEM照片
Figure 6 SEM images of NH2-MIL-101 (a) and NH2-FMOF-CFIL (b)
图 7 N2吸附-脱附曲线 (a) 和BJH孔径分布 (b)
Figure 7 (a) N2 adsorption/desorption isotherms and (b) BJH pore size distribution
图 8 NH2-MIL-101和NH2-FMOF-CFIL的TGA曲线 (a) 和DTG曲线 (b)
Figure 8 TGA (a) and DTG curves (b) of NH2-MIL-101 and NH2-FMOF-CFIL
图 9 CFIL、NH2-MIL-101和NH2-FMOF-CFIL在0.1 MPa、40 ℃下的催化性能
Figure 9 Catalytic performance of CFIL, NH2-MIL-101 and NH2-FMOF-CFIL in the cycloaddition of CO2 with epichlorohydrin at 0.1 MPa and 40 ℃ for 24 h
图 10 NH2-FMOF-CFIL在0.1 MPa、24 h、不同温度下的催化性能
Figure 10 Effect of temperature on the cycloaddition of CO2 with epoxides to cyclic carbonates over NH2-FMOF-CFIL at 0.1 MPa for 24 h
图 11 NH2-FMOF-CFIL在0.1 MPa、70 ℃、24 h下的催化循环性能
Figure 11 Cyclic performance of the NH2-FMOF-CFIL catalyst in CO2 cycloaddition at 0.1 MPa, 70 ℃ and 24 h
图 12 NH2-FMOF-CFIL新鲜和回收后的FT-IR (a) 和PXRD谱图 (b)
Figure 12 FT-IR spectra (a) and PXRD patterns (b) of fresh and recovered NH2-FMOF-CFIL
图 13 NH2-FMOF-CFIL催化机理示意图
Figure 13 Proposed catalytic reaction mechanism for the cycloaddition of CO2 with epoxides to cyclic carbonates over NH2-FMOF-CFIL
表 1 样品中N、C、O、H的质量分数
Table 1 Contents of N, C, O and H in various samples
Sample Content /% ILs / N C O H NH2-H2BDC NH2-MIL-101 3.67 30.06 35.32 3.73 0 NH2-FMOF-CFIL 6.85 38.12 30.75 4.13 1∶4 
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表 2 NH2-MIL-101 和 NH2-FMOF-CFIL结构参数
Table 2 Textural properties of NH2-MIL-101 and NH2-FMOF-CFIL
Sample SBET/ (m2·g−1) vtotal/ (cm3·g−1) NH2-MIL-101 1586 0.73 NH2-FMOF-CFIL 1032 0.88
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