Magnetically recyclable Fe3O4@SiO2 supported phosphonium ionic liquids for efficient and sustainable transformation of CO2 into oxazolidinones

Yu Lin Hu; Qiu Yun Zhang; Yu Tao Zhang

doi:10.1515/gps-2024-0180

Article Open Access

Magnetically recyclable Fe₃O₄@SiO₂ supported phosphonium ionic liquids for efficient and sustainable transformation of CO₂ into oxazolidinones

Yu Lin Hu , Qiu Yun Zhang and Yu Tao Zhang

Published/Copyright: November 19, 2024

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From the journal Green Processing and Synthesis Volume 13 Issue 1

Abstract

Carbon dioxide (CO₂) as a C1 building block to synthesize 2-oxazolidinones is an environmental and sustainable approach. In this work, we present the synthesis and characterization of novel heterogeneous catalysts by immobilizing homogeneous phosphonium ionic liquids (ILs) onto magnetic Fe₃O₄@SiO₂, which could realize the cycloaddition of CO₂ and a range of aziridines into 2-oxazolidinones under mild conditions of 90°C and 1 atm CO₂ pressure. The immobilized IL Fe₃O₄@SiO₂@PILCeCl₄ demonstrated remarkable catalytic activity in the CO₂ transformation, leading to high to excellent yields (87–95%) as well as excellent selectivities (98–99.2%) in the absence of solvent at reaction times of 8–10 h, from alkyl- or aryl-substituted and N-alkyl-substituted aziridines. The heterogeneous and magnetic nature of the catalyst facilitated effortless recovery and efficient reusability, which could be easily separated and reused up to five consecutive cycles without considerable decrease in catalytic activity. This protocol provides a novel and efficient strategy for producing 2-oxazolidinones, with potential applications in chemical transformation of CO₂ into value-added chemicals.

Graphical abstract

Keywords: carbon dioxide transformation; supported ionic liquid; oxazolidinones; synergistic catalysis; ecofriendly green protocol

1 Introduction

Carbon dioxide (CO₂), as the major culprit of global warming, has drawn widespread attention because its continuous accumulation causes human health and ecological problems [1,2]. Carbon capture and storage technologies aim to reduce the amount of CO₂ released into the atmosphere and utilization of CO₂ as a feedstock for chemical synthesis presents an attractive route to mitigate emissions while producing valuable products [3,4]. Converting CO₂ into useful chemicals, fuels, and materials not only helps in managing carbon emissions but also promotes the development of a circular carbon economy [5–8]. Amongst various approaches, the cycloaddition reaction of CO₂ with aziridines has high atom economy, and the products 2-oxazolidinones can be used in applications such as in natural product synthesis, pharmaceuticals, and auxiliaries [9]. Currently, CO₂ cycloaddition catalysts have been designed for producing 2-oxazolidinones via the cycloaddition reaction of CO₂ with aziridines, such as 2,2′′,2″-terpyridine [10], TPPH₂@SBA-15 [11], MO_x(acac)_n/TBAB [12], MOFs [13–15], catechol porphyrin COF [16], HKUST-1/TBAB [17], amine functionalized MCM-41 [18], and others [19–21]. Although significant progress has been made, most reported catalyst systems suffer from a number of drawbacks, including high temperature, lengthy preparation, the need for co-catalysts and solvents, long reaction time, high CO₂ pressure, and use of expensive reagents. Therefore, the development of novel and efficient catalytic systems that promote the cycloaddition reaction of CO₂ with aziridines under mild conditions remains a pressing research topic.

Ionic liquids (ILs) have garnered considerable attention due to their distinctive properties, including negligible vapor pressure, high thermal stability, a wide liquid temperature range, easy recyclability, excellent chemical stability, and strong solvent capabilities for various organic and inorganic molecules [22–28]. Furthermore, magnetic ILs have garnered particular interest for their paramagnetic ability to facilitate separation and recovery of catalyst during catalytic reactions by using an external magnetic field [27,28]. Recently, several catalytic systems of ILs have been developed for converting CO₂ into 2-oxazolidinones [29,30]. However, these catalysis systems often lack cyclic stability and suffer from the difficult separation of product and catalysts, which was limited in practical application. Thus, combining the advantages of ILs and the heterogeneous catalysts to synthesize the immobilization of ILs onto porous materials is highly desirable for producing 2-oxazolidinones. To achieve efficient conversion and separation, some researchers designed a variety of ILs immobilized on numerous porous materials (mesoporous materials, porous carbon, magnetite nanoparticles, etc.) [31–35]. Magnetite nanoparticles, especially Fe₃O₄@SiO₂ have a large surface area and core–shell structure, providing more active sites [36–40]. Immobilizing ILs on the surfaces of these magnetite materials can increase the IL load, thereby increasing the contact area between the active sites and the substrates, leading to enhanced catalytic performance and reduced separation step via an external permanent magnet. In continuation of our research on the introduction of novel and recoverable catalysts in chemical fixation of CO₂ into 2-oxazolidinones, in the current study, a type of magnetic supported phosphonium ILs through a covalent bond linkage were successfully prepared and used as heterogeneous catalysts for the cycloaddition reaction of CO₂ with aziridines under solvent- and cocatalyst-free conditions, showcasing easy manipulation, easily recovery from the reaction mixture, excellent stability, and reusability.

2 Experimental

2.1 Synthesis of supported phosphonium ILs

The magnetic supported phosphonium ILs were synthesized by the modified reported methods [34–38], and the detailed procedures are outlined in supporting information.

2.2 Typical procedure for the synthesis of 2-oxazolidinones

In a representative experiment, aziridine (10 mmol) and Fe₃O₄@SiO₂@PILCeCl₄ (0.5 g) were added into a 20 mL autoclave reactor with an internal Teflon insert. The system was purged with CO₂ three times and then the mixture was stirred at a given temperature for the desired time and CO₂ was provided by balloon (0.1 MPa). The reaction progress was determined by gas chromatograph (GC; Agilent 7890A) using styrene as an internal standard. After the reaction was completed, the reactor was cooled to room temperature. The product was then dissolved in dichloromethane, and the supported catalyst Fe₃O₄@SiO₂@PILCeCl₄ was recovered from the reaction medium by simple external magnet and washed several times with ethanol. The recovered catalyst was dried under vacuum at 50°C overnight before being used for the next run under identical reaction conditions. The filtrate was concentrated under vacuum to give the pure products. The desired products are commercial, and were investigated by comparison with those of standard compounds, ¹H NMR, and elemental analysis (supporting information).

3 Results and discussion

The crystalline phase of supported phosphonium ILs was investigated by the powder X-ray diffraction (Figure 1). The characteristic diffraction peaks appearing at 2θ = 30.2°, 35.6°, 43.3°, 53.8°, 57.2°, 62.8°, and 74.5° were attributed to (220), (311), (400), (422), (511), (440), and (533) crystal planes of Fe₃O₄ nanospheres, respectively (JCPDS Card No. 72-2303). The peaks at 2θ = 22–23° were attributed to the (02–2) plane of amorphous SiO₂ shells (JCPDS Card No. 38-0651). It could be seen that the nanocomposites had strong diffraction peaks of Fe₃O₄@SiO₂ nanospheres while the other diffraction peaks of organic IL moieties were very weak, indicating that the crystal phase of the nanomaterials was uniform and the crystal size was large. Therefore, it can be inferred that the magnetic nanocomposites have been successfully prepared without damaging the crystalline cubic spinel structure of Fe₃O₄@SiO₂ core.

Figure 1

XRD pattern of (a) Fe₃O₄@SiO₂@PILAlCl₄, (b) Fe₃O₄@SiO₂@PILMgCl₃, (c) Fe₃O₄@SiO₂@PILCeCl₄, and (d) Fe₃O₄@SiO₂.

The morphology and microstructure characteristics of the supported phosphonium IL nanocomposites were characterized through SEM (Figure 2). As can be observed, Fe₃O₄@SiO₂ presents regularly sized particles with rounded edges morphology typical of magnetic particles [37–39]. The particle size of the Fe₃O₄@SiO₂ confined in the magnetic nanoparticles is similar to the particle size of supported phosphonium IL nanocomposites, indicating that the silica gel particles have good mechanical stability during the nanocomposites synthesis and confinement step. In addition, as can be seen in the micrographs of Fe₃O₄@SiO₂ and supported IL nanocomposites, there is no change in the morphology of the magnetic silica crystals after the immobilization of phosphonium IL organic moieties. The supported ILs and pure Fe₃O₄@SiO₂ support were also confirmed using the EDX spectrum (Figure 3). EDX results further demonstrated the successful immobilization of phosphonium ILs on the Fe₃O₄@SiO₂ support. In addition, the element mappings confirm the uniform distribution of the main elements of Fe, Si, O, P, C, Cl, Al, Mg, and Ce in the synthesized supported IL nanocomposites. The FT-IR spectra of the synthesized supported IL nanocomposites are depicted in Figure S1. It can be seen from the figure that the stretching vibration peaks of Si–O–Si and Si–OH at about 3,500–3,340, 1,092–1,078, and 978–972 cm⁻¹ are significant in all the supported ILs. The characteristic peaks at 3,049–3,046 and 1,631–1,625 cm⁻¹ are attributed to the stretching vibration of C═C and C–H on the phenyl rings, and the peaks at around 1,312 and 908 cm⁻¹ were assigned to the vibration of C–P [25,32–34]. The peaks at around 2,960, 2,943, 2,872 and 2,854 cm⁻¹ correspond to the stretching vibrations of CH₃ and CH₂, respectively. The peak appearing at 581–573 cm⁻¹ corresponds to the stretching vibration of the Fe–O–Fe group of magnetic particles. UV–Vis spectra of the supported IL nanocomposites are shown in Figure S2. The typical absorption bands located at 217–226 nm are attributed to the absorption properties of Fe–O atoms in the nanocomposites. The bands around 258–267 and 364–400 nm are identified as the absorption properties of Mg–Fe atoms (Figure S2b). In the spectrum of Fe₃O₄@SiO₂@PILCeCl₄, two distinctive absorption bands at 237–280 and 332–400 nm are identified as the absorption properties of Ce–Fe atoms (Figure S2c) [41–44]. The characteristic signals corresponding to ILs were not observed in the patterns, probably due to the low amount ratio and uniform distribution of the organic moieties in the framework.

Figure 2

SEM images of (a) Fe₃O₄@SiO₂@PILAlCl₄, (b) Fe₃O₄@SiO₂@PILMgCl₃, (c) Fe₃O₄@SiO₂@PILCeCl₄, (d) Fe₃O₄@SiO₂, and (e) five times recycled Fe₃O₄@SiO₂@PILCeCl₄.

Figure 3

EDX images of Fe₃O₄@SiO₂@PILAlCl₄, (b) Fe₃O₄@SiO₂@PILMgCl₃, (c) Fe₃O₄@SiO₂@PILCeCl₄, and (d) Fe₃O₄@SiO₂.

To evaluate the catalytic performance of supported phosphonium ILs for cycloaddition reactions, 2-methylaziridine was selected as a model substrate to obtain the expected product 5-methyloxazolidin-2-one, and the findings are shown in Table 1. First, the effect of synthesized supported phosphonium IL catalysts was checked (Table 1, entries 1–3). Under the same conditions, the product yield was 93% using the catalyst Fe₃O₄@SiO₂@PILCeCl₄ (Table 1, entry 3), which indicated that Fe₃O₄@SiO₂@PILCeCl₄ was slightly better than Fe₃O₄@SiO₂@PILAlCl₄ and Fe₃O₄@SiO₂@PILMgCl₃. In comparison, the catalytic activities were significantly decreased after treatment with bulk ILs of PILAlCl₄, PILMgCl₃, PILCeCl₄, and PILCl as catalysts (Table 1, entries 4–7), achieving yields of 73%, 54%, 88%, and 65% for 5-methyloxazolidin-2-one, respectively. We also investigated the catalytic efficiency of the bare support Fe₃O₄@SiO₂, demonstrating that the support was not an effective catalyst for the reaction (Table 1, entry 8). In addition, the effect of the Fe₃O₄@SiO₂@PILCeCl₄ catalyst amount was examined on the mentioned reaction. As shown in the table, no target product was generated without any catalyst (Table 1, entry 9). With the increase of catalyst amount, the catalytic cycloaddition effect was obviously improved (Table 1, entries 10–12), the product yield gradually increased to reach 93% at 0.5 g catalyst amount. And the continuous increase of catalyst amount did not significantly increase the product yield (Table 1, entry 13). It was observed that 0.5 g of Fe₃O₄@SiO₂@PILCeCl₄ catalyst demonstrated the best performance in catalyzing the cycloaddition reaction with excellent yield (93%) and selectivity (99.1%) toward the desired product.

Table 1

Catalysts screening for cycloaddition of CO₂ and 2-methylaziridine^a

Entry	Catalyst	Catalyst (g)	Time (h)	Yield (%)^b	Selectivity (%)^c
1	Fe₃O₄@SiO₂@PILAlCl₄	0.5	10	79	94.8
2	Fe₃O₄@SiO₂@PILMgCl₃	0.5	10	52	91.7
3	Fe₃O₄@SiO₂@PILCeCl₄	0.5	8	93	99.1
4	PILAlCl₄	0.5	12	73	92.6
5	PILMgCl₃	0.5	12	54	90
6	PILCeCl₄	0.5	12	88	97.4
7	PILCl	0.5	12	65	93.7
8	Fe₃O₄@SiO₂	1.0	24	Trace	—
9	—	—	24	0	—
10	Fe₃O₄@SiO₂@PILCeCl₄	0.1	15	62	96.4
11	Fe₃O₄@SiO₂@PILCeCl₄	0.3	8	75	97.5
12	Fe₃O₄@SiO₂@PILCeCl₄	0.4	8	87	98.3
13	Fe₃O₄@SiO₂@PILCeCl₄	0.6	6	94	98.6

^aReaction conditions: 2-methylaziridine (10 mmol), CO₂ balloon (1 atm), 90°C. ^bIsolated yield. ^cGC analysis.

The effect of reaction parameters on the CO₂ cycloaddition was examined with a focus on reaction temperature and reaction time. As shown in Figure 4a, the yield of 5-methyloxazolidin-2-one on Fe₃O₄@SiO₂@PILCeCl₄ catalyst increases as the temperature rises from 50°C to 90°C. This is because the temperature can provide energy for the reaction process, which can activate CO₂ and promote the ring opening of 2-methylaziridine. The product yield reaches 93% at 90°C for 8 h and selectivity remains consistently at 99.1%. As the temperature further increased, the product yield and selectivity were slightly decreased owing to the formation of side products at higher temperatures. Therefore, 90°C is chosen as the optimal reaction temperature. As shown in Figure 4b, in order to explore the optimum reaction time at 90°C, the cycloaddition reaction was carried out at different times. Increasing the reaction time can effectively improve the catalytic conversion through increasing the effective collision. Expectedly, advancing reaction time to 8 h led to the maximum product yield. However, further increasing the reaction time above 8 h was insignificant to improve the product yield. Therefore, the optimum reaction time is 8 h.

Figure 4

Effect of synthesis conditions on the catalytic activity of Fe₃O₄@SiO₂@PILCeCl₄: (a) temperature: 2-methylaziridine (10 mmol), Fe₃O₄@SiO₂@PILCeCl₄ (0.5 g), CO₂ balloon (1 atm), 8 h; (b) time: 2-methylaziridine (10 mmol), Fe₃O₄@SiO₂@PILCeCl₄ (0.5 g), CO₂ balloon (1 atm), 90°C.

Furthermore, the magnetic properties of Fe₃O₄@SiO₂ and the superior catalyst Fe₃O₄@SiO₂@PILCeCl₄ were investigated using vibrating sample magnetometer analysis at room temperature (Figure S3). It could be seen that Fe₃O₄@SiO₂ has a saturation magnetization value of 31.7 emu·g⁻¹, and the catalyst Fe₃O₄@SiO₂@PILCeCl₄ value decreases to 13.9 emu·g⁻¹ because of the immobilization modification of IL. The two samples display no hysteresis loop in their magnetic behavior, indicating their superparamagnetic characteristics and also revealing the attractive recovery application of a simple external magnet, so the catalyst Fe₃O₄@SiO₂@PILCeCl₄ could be easily separated and recovered from the reaction medium by simple external magnet. The recyclability of Fe₃O₄@SiO₂@PILCeCl₄ catalyst was also demonstrated for producing 5-methyloxazolidin-2-one under the optimum reaction conditions and the result is shown in Figure 5a. It was found to be effective up to five consecutive runs with no significant loss in its catalytic activity, indicating that the catalyst has good stability and reusability. In order to get an insight into the stability of Fe₃O₄@SiO₂@PILCeCl₄ catalyst, the leaching experiments were carried out and the results are displayed in Figure 5b. It was observed that there was no obvious improvement in product yield after the catalyst was removed after 4 h during the catalytic process, indicating that the catalyst has good stability. In addition, the XRD pattern of the recycled catalyst after five runs did not show significant change with respect to those of a fresh catalyst (Figure S4). Moreover, SEM image of Fe₃O₄@SiO₂@PILCeCl₄ catalyst was performed before and after five cycles (Figure 2e), and the results showed that no obvious change was observed in the morphology, indicating the good stability of the catalyst. The above results evidenced the high efficiency and recyclability of this two-component catalytic system. Conclusively, Fe₃O₄@SiO₂@PILCeCl₄ can be used as a highly efficient catalyst with good recyclability for the CO₂ cycloaddition reaction under mild conditions.

Figure 5

(a) Reusability studies of the Fe₃O₄@SiO₂@PILCeCl₄ catalyst and (b) leaching experiment of cycloaddition reaction.

With optimized reaction conditions in hand, the generality of this protocol was investigated using other aziridines (Table 2). It could be seen that a series of aziridines with different steric and electronic effects could be quantitatively converted into the corresponding 2-oxazolidinones in excellent yields (87–95%) and selectivities (98–99.2%) under solvent-free conditions, demonstrating that the catalyst has broad universality of substrate. It is noteworthy that the substrates containing N-substituted groups showed lower yields of 87–89% with a longer reaction time of 10 h, which may be one of the reasons for its steric hindrance effect (Table 2, entries 5–8).

Table 2

Catalytic cycloaddition reaction of CO₂ and aziridines under optimized conditions^a

Entry	Time (h)	Yield (%)^b	Selectivity (%)^c
1	8	93	99.1
2	8	95	99.2
3	8	92	98.7
4	8	91	99
5	10	89	98.1
6	10	88	98.2
7	10	87	98.5
8	10	89	98

^aReaction conditions: Aziridine (10 mmol), Fe₃O₄@SiO₂@PILCeCl₄ (0.5 g), CO₂ balloon (1 atm), 90°C. ^bIsolated yield. ^cGC analysis.

The comparative catalytic activity of the present catalytic system with previously reported catalytic systems is summarized in Table S1. It could be seen that the Fe₃O₄@SiO₂@PILCeCl₄ catalyst has an excellent catalytic performance compared to the previously reported systems in terms of reaction conditions and product yield. The results showed that the present catalyst not only exhibited excellent catalytic activity but also was more green and friendly.

Based on the reported literature [14–17,30] and catalytic results, we propose a possible mechanism for cycloaddition reaction of CO₂ and aziridines over Fe₃O₄@SiO₂@PILCeCl₄ catalyst (Figure 6). First, CO₂ can be captured and activated by the nitrogen atom of aziridine to form intermediate I. Next, the Si-OH species of Fe₃O₄@SiO₂@PILCeCl₄ catalyst bind with the oxygen atom of intermediate I followed by a nucleophilic attack with CeCl₄ anion mainly at the less sterically hindered C atom of activated aziridine to form intermediate II. Subsequently, intermediate II underwent an intramolecular nucleophilic substitution reaction to form intermediate III. Finally, the corresponding 2-oxazolidinone was produced through an intramolecular cyclization reaction, and the synergistic catalyst was regenerated in the process for the next cycle.

Figure 6

Proposed reaction mechanism for the synthesis of 2-oxazolidinones.

4 Conclusions

In this study, we successfully used the magnetic supported phosphonium ILs as green catalysts to catalyze the cycloaddition of CO₂ and aziridines under mild and solvent-free conditions. The experiments showed that the catalyst Fe₃O₄@SiO₂@PILCeCl₄ activates CO₂ and aziridine for efficient conversion into 2-oxazolidinone products in high to excellent yields and selectivities, probably due to the coexistence of synergistic effect between IL and magnetic support. The supported IL Fe₃O₄@SiO₂@PILCeCl₄ demonstrated excellent recyclability, maintaining its catalytic activity over five cycles without any significant decline. The developed methodology offers several advantages including high efficiency, very good yield and excellent selectivity, and environmental compatibility with high atom economy. We expect that this work can offer some ideas for designing new and efficient methodologies rationally in order to convert CO₂ into high value-added chemicals at atmospheric pressure.

Acknowledgements

The authors gratefully acknowledge the support provided by the College of Chemistry and Chemical Engineering, Anshun University for providing the facilities during the research.

Funding information: The research was funded by the National Natural Science Foundation of China (22368001), Key Laboratory of Agricultural Resources and Environment in High Education Institute of Guizhou Province (Qianjiaoji[2023] 025) and Porous Materials and Green Catalysis Innovation Team of Institutions of Higher Education of Guizhou Province (Qianjiaoji [2023]086).
Author contributions: Yu Lin Hu: conceptualization, investigation, data collection, formal analysis, methodology, writing – original draft, writing – review and editing, and visualization; Qiu Yun Zhang: project administration and formal analysis; Yu Tao Zhang: project administration, conceptualization, supervision, formal analysis, methodology, validation, and writing – review and editing.
Conflict of interest: The authors state no conflict of interest.
Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2024-08-12

Accepted: 2024-10-17

Published Online: 2024-11-19

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/gps-2024-0180

Keywords for this article

carbon dioxide transformation; supported ionic liquid; oxazolidinones; synergistic catalysis; ecofriendly green protocol

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Magnetically recyclable Fe3O4@SiO2 supported phosphonium ionic liquids for efficient and sustainable transformation of CO2 into oxazolidinones

Article

Abstract

Graphical abstract

1 Introduction

2 Experimental

2.1 Synthesis of supported phosphonium ILs

2.2 Typical procedure for the synthesis of 2-oxazolidinones

3 Results and discussion

4 Conclusions

Acknowledgements

References

Supplementary Material

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Magnetically recyclable Fe₃O₄@SiO₂ supported phosphonium ionic liquids for efficient and sustainable transformation of CO₂ into oxazolidinones