Sustainable Production of Cyclic Carbonates from CO 2 and Epoxides Using Transition Metal Substituted Polyoxometalate-TBA Hybrid Catalysts

doi:10.21203/rs.3.rs-3569762/v1

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Sustainable Production of Cyclic Carbonates from CO 2 and Epoxides Using Transition Metal Substituted Polyoxometalate-TBA Hybrid Catalysts

https://doi.org/10.21203/rs.3.rs-3569762/v1

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Transition metal substituted polyoxometalates (TMS-POMs) are well recognized for their catalytic characteristics due to their fascinating chemical and physical properties resulting from unparalleled adaptability and structural variety. The interaction of these TMS-POMs with the bulky organic cations enhances the catalytic efficiency with the change in morphology. In this work, we used three hybrid materials of transition metal (Co²⁺, Ni²⁺, Cu²⁺) substituted lacunary Keggin polyoxometalate with tetrabutylammonium cations. The formation and structural features of hybrid materials have been studied by powder XRD, TGA, SEM, TEM, FTIR, and ³¹P NMR. These hybrid catalysts have been used for the atom-economic coupling of carbon dioxide (CO₂) with epoxides to produce cyclic carbonates at incredibly mild circumstances, such as room temperature and atmospheric pressure. The method described here allows for the rapid and effective quantitative conversion of several aliphatic, cyclic, and aromatic epoxides to their respective cyclic carbonates in solvent-free conditions. The cobalt substituted hybrid catalyst shows the highest activity and selectivity with a minimum quantity of 0.12 mol% adequate to provide 85% conversion in 3 h at room temperature. The catalyst is recovered and reused up to four cycles without a drastic loss in activity, hence providing long-term solutions for climate change and environmental concerns.

Chemical fixation of CO2

epoxides

cyclic carbonates. Tetrabutylammonium cations

TMS-POM-TBA hybrid materials

green chemistry

The chemical fixation of CO₂ is a paradigmatic solution for the challenges related to growing energy demand and global warming [1]. Utilising CO₂ (combustion waste), a potential carbon feedstock for the manufacture of chemicals and fuels is construed as one of the virtuous areas of research [2–3]. CO₂ is thermodynamically stable molecule. A significant energy barrier must be crossed for its activation and conversion into other organic molecules. The dissociation energy of a C = O bond in CO₂ is 750 kJ mol^− 1 which is higher than other bonds, such as C−H (430 kJ mol^− 1) and C−C (336 kJ mol^− 1) [4]. The efficiency of CO₂ conversion processes thus mostly depends on the nature of catalyst. In this context, the most efficient use of CO₂ is the direct production of cyclic carbonates from CO₂ and epoxides [5–6]. Cyclic carbonates have been widely used as aprotic solvents, biomedical precursors, and engineering polymers due to their fascinating qualities of high boiling point, low toxicity, high solubility, and biodegradability [7–11]. A number of catalyst materials including metal/organic-supported complexes, metal oxides, organic and inorganic bases, phosphines, salen complexes, porous catalysts, titanosilicates, ionic liquids, and zeolites have been employed for converting CO₂ to epoxides [12–16]. However, in the majority of these conversion processes extreme conditions such as high temperature and pressure have been used to obtain satisfactory yields [17–19]. The search for synthetic methods towards cyclic carbonates under atmospheric pressure is garnering special interest [20–30]. Although many of these findings provide conversion of CO₂ at atmospheric pressure, they all needed high reaction temperature, costly and homogeneous catalysts. Transition metal substituted polyoxometalates (TMS-POMs) can be the alternatives because of the distinct characteristic of the substituted metal to activate the ring opening of electron rich epoxides enhanced by the electron withdrawing nature of the surrounding substituted polyoxometalate, to convert CO₂ non-reductively into cyclic carbonates [31–34].

Polyoxometalates (POMs) are a diverse family of anionic metal-oxo clusters with unparalleled versatility in both structure and functions, making them potential catalysts or co-catalysts [35–40]. The Keggin type POMs are the most stable and sought-after form of polyoxometalate. The mono- and polylacunary Keggin-type POMs with enhanced anionic charges and nucleophilic oxygen-enriched surfaces originate from the removal of a variable number of metal-oxide octahedral from the plenary polyanion, by varying pH [41–43]. Such lacunary POMs have complex substitution chemistry at the defect site, generating a completely new set of transition metal substituted polyoxometalate (TMS-POMs) with enhanced catalytic properties and stability, depending on the metal ion substituted [44].

Usually, the potential of POMs as effective and ecologically friendly catalysts is constrained by their high solubility, small surface area, low recovery and recycling rates hence needs support like, MOFs, inorganic complexes, inorganic polymers, for harvesting the maximum efficiency [45–46] The intrinsic anionic charge of the nucleophilic surface of TMS-POMs can be stabilized by integrating them with bulky organic counter cationic groups. This provides a flexible approach for the formation of organic-inorganic hybrid materials at nanosomic dimensions with efficient and adjustable properties [47, 43]. The POM-based compounds function as effective catalysts as they have a unique property of attracting electrons from electron donating substrates like epoxides and activates the acidic CO₂ for addition on the metal substituted site in TMS-POM [48, 49]. In this work, we have prepared three heterogeneous hybrid materials containing TMS-POM anions and bulky organic moiety (tetrabutylammonium bromide) as counter cation (TBA-PWCo, TBA-PWNi, and TBA-PWCu) and used them as catalysts for the synthesis of cyclic carbonates via cycloaddition of CO₂ and epoxides, under solvent free and ambient conditions. These TMS-POM-hybrid materials are found to be active, selective, stable and sustainable heterogeneous catalysts for CO₂ conversion under ambient conditions. Among them, the TBA-PWCo is the most effective catalyst for cyclic carbonate formation.

2.1. Materials

Sodium tungstate dihydrate (Na₂WO₄ .2H₂O) was bought from Avra Laboratories, India. Disodium hydrogen phosphate (Na₂HPO₄), phosphotungstic acid (H₃PW₁₂O₄₀) and nitrate salts of cobalt, nickel and copper were purchased from Thermo Fisher Scientific, India. Tetrabutylammonium bromide (TBAB) was supplied by Aldrich. All the epoxides used in CO₂ conversion were purchased from Avra Scientific Company.

2.2 Materials characterization

The JASCO FT/IR 4100 spectrometer was used to record FTIR spectra of hybrid materials, using KBr pellet technique. The materials were examined in the UV-visible region between 200 and 800 nm using a JASCO V-660 spectrometer and BaSO₄ as a reference. Bruker D8 Advance X-ray diffractometer with CuK (λ = 0.15406 nm) radiation was used to acquire powder X-ray diffraction (PXRD) patterns of the hybrid materials. The microscopic examinations were conducted by the FEI Quanta 200F electron microscope. The samples were submitted to thermogravimetric analysis (TGA) in a nitrogen-flowing Perkin-Elmer TGA Q500 system. A Bruker-FT-NMR 400 MHz spectrometer was used to conduct solid-state ³¹P NMR studies of the hybrid catalyst materials. The catalytic conversions of CO₂ to cyclic carbonates were analysed by ¹H NMR spectra recorded on Bruker-FT-NMR 500 MHz spectrometer by dissolving the reaction mixtures in CDCl₃ solvent. JEOL Japan, JEM-2100 Plus was used to carry out the TEM analysis of the TBA-PWCo sample.

2.3 Synthesis of hybrid TBA-TMS-POM hybrid materials

In situ Keggin-based TMS-POM hybrid catalyst synthesis has been carried out according to the literature report [37]. Standard procedures involved dissolving 2.0 mmol of disodium hydrogen phosphate, 25 mmol of sodium tungstate, and 3 mmol of metal nitrate (Co²⁺, Ni²⁺, and Cu²⁺) in 50 ml of distilled water. The pH of the solution was then adjusted to 4.8, using 1.0 M HNO₃ solution. The transition metal-substituted Keggin ions form in the resulting solution. Then, 11.2 mmol of TBAB solution was added to the aforementioned solution. The reaction was conducted for an hour under constant stirring. The resultant precipitate was filtered, washed with distilled water and dried overnight in vacuum oven at 60°C. These hybrid materials are referred to as TBA-PWCo, TBA-PWNi, and TBA-PWCu, based on the respective substituted metals. All the three hybrid materials have a subtle, powdery texture. The compounds exhibit distinctive colours associated with the substituted transition metal ions in the Keggin units (Fig. 1).

3.1 Physicochemical Characterization

The FT-IR spectra of the three TBA-TMSPOM hybrid materials are shown in Fig. 2. The IR spectra of pure phosphotungstic acid and TBAB are also plotted in order to compare with the Keggin signature peaks and TBA peaks coexisting in the hybrid material. The peaks at 807, 892, 988, and 1080 cm^− 1 are due to the stretching frequencies \({\nu _{\left( {W - {O_e} - W} \right)}}\), \({\nu }_{(W-{O}_{c}-W)}\), \({\nu }_{(W={O}_{ter} )}\) and \({\nu }_{(P-O)}\)which suggest the formation of intact Keggin structures [37]. The ν (\(\text{P}-\text{O}\)) vibration peak at 1080 cm⁻¹ shows a split arising from the asymmetry in the PO₄ tetrahedral unit as a result of metal substitution in the Keggin moiety [49, 50]. The –CH₂ and -CH₃ stretching frequencies found in the TBA moiety are responsible for the distinctive absorption bands at 2849 cm^− 1 and 2963 cm^− 1.

Polyoxometalates exhibit noticeable oxygen-to-metal charge transfer bands in the UV region [51]. The UV-visible spectra of hybrid materials and their parent compounds are shown in Fig. 3. The charge transfer peaks from oxygen to tungsten in the Keggin moiety are seen at 210 nm, 260 nm and 310 nm. The hybrid materials showed significant absorption bands in the lower energy region spanning between 600–800 nm extending to near IR, corresponding to the substituted 3d transition metals in the Keggin units. These broad features are due to the spin-allowed d-d transitions with configurations of d⁷ (Co²⁺), d⁸ (Ni²⁺) and d⁹ (Cu²⁺) ions in the Keggin moieties of respective hybrid materials. The bromide peaks observed in the pure TBAB [52] (Fig. 3(e)) are not observed in the hybrid materials, suggesting the formation of hybrids with TBA cations and TMS-POMs anions by replacing bromide ions of TBAB.

The hybrid materials are further characterized by TGA to analyse their thermal stability and decomposition pattern. All the hybrid materials exhibit a similar stepwise degradation trend, as shown in Fig. 4. The hybrid materials show small weight loss till 120°C, due to the loss of bound water molecules. The materials are stable up to 250°C, after which they show a two-step decomposition corresponding to the loss of TBA moiety between 300–450°C and 600–750°C [53]. Tetrabutylammonium bromide is a purely organic compound that decomposes completely in two steps at temperatures ranging from 350 to 550°C [53]. The strong electrostatic interaction between Keggin anions and bulky TBA cations is the reason for the increased thermal stability of TBA in hybrid materials. Each metal substituted Keggin (PW₁₁O₃₉ M)^5- interacting with five units of tetrabutylammonium cations results in a 20–25% weight loss in all hybrid products.

Phosphotungstic acid is highly crystalline material. The powder XRD pattern of PWA and hybrid materials are shown in Fig. 5. Unlike PWA, the hybrids did not show any sharp peaks at higher angle region, while a set of new intense peaks are seen below 2θ = 10°. This indicates that the hybrids are amorphous and have short range order [54, 38]. The materials have d-spacing of almost 1.5 nm and the particle size of these materials range from 10–30 nm as calculated by Scherrer equation.

Further the surface morphologies of the synthesized hybrid materials were examined through SEM. The SEM images shown in Fig. 6, corroborates with the amorphous nature of the materials as interpreted from the powder XRD patterns. The TBA-PWCo hybrid shown in Fig. 6(a), has some distinctive non-uniform particle like morphology while the TBA-PWNi hybrid shown in Fig. 6(b), has non uniform elongated particles with distorted and irregular edges. The TBA-PWCu hybrid has fine particulate morphology with soft edges, as seen in Fig. 6(c). The metal substitution and functionalization with TBA resulted in the changes in morphology when compared to pure crystalline PWA. The respective EDAX patterns and elemental compositions of the hybrid materials confirms the proposed molecular structures from thermal analyses.

The amorphous nature of these hybrid catalysts can also be confirmed by HRTEM analysis. The HRTEM images of TBA-PWCo catalyst are shown in Fig. 7 (a and b) at various magnifications. The SAED pattern shown in Fig. 7(c) has diffused rings, indicating the amorphous nature of the materials. The elemental composition of the hybrid obtained from EDX is shown in Fig. 7(d) is in support of the proposed molecular structure.

The transition metal substituted Keggin anions were in situ generated during the synthesis of hybrid materials. The structure can further be established from ³¹P NMR. The phosphorous present in unsubstituted Keggin, (PW₁₂O₄₀)^3-, shows a peak at -15 ppm in ³¹P NMR [55]. The vacancy present in the monolacunary Keggin, (PW₁₁O₃₉)^7-, deshields the phosphorous to a chemical shift of -10 ppm [56, 54]. The presence of metal substitution in the lacunary site of Keggin in hybrid materials, partially shielded the phosphorous to around − 13.7 ppm [57], as shown in Fig. 8. Therefore, the formation of transition metal substituted Keggin is confirmed.

3.2 TBA-TMSPOM catalysed conversion of CO₂ to cyclic carbonates

TBA-TMSPOM hybrid materials are employed as heterogeneous catalysts for the chemical transformation of CO₂ into cyclic carbonates, under mild reaction conditions. Typically, 5 mmol of epoxide, 0.12 mol of TBA-TMSPOM hybrid material as catalyst and 0.5 mmol of TBAB as a co-catalyst were placed into a round bottom flask with a CO₂ balloon. This cycloaddition process was allowed to proceed for 4 hours at room temperature without solvent. Following the completion of the reaction, ethyl acetate was added to the reaction mixture and then centrifuged to recover the catalyst from the organic mixture. The crude organic mixture was then washed with water before being dried over anhydrous Na₂SO₄. The ethyl acetate was evaporated to obtain the crude product, and the substrate conversion was then determined by NMR analysis of the crude product. During the screening studies, substrate scope, and recyclability experiments, the ¹H-NMR of the crude reaction mixture furnished data pertaining to substrate conversion and selectivity. The outcomes are summarized in Chart 1.

The cycloaddition of CO₂ to epichlorohydrin was chosen as the model experiment for our optimization studies (Scheme 1). As presented in Chart 1(a), the desired product was not generated when the reaction lacked both catalyst and co-catalyst, while TBAB converted 35% of the substrate without TBA-PWCo. The catalytic system of 0.12 mol of TBA-PWCo and 0.5 mmol of TBAB reaction resulted in giving substrate conversion of 85% (Figure S1). This evidently demonstrates that TBA-TMSPOMs are far more efficient at cycloaddition and the data shows that the reaction proceeds with little or no side products and good selectivity. Combinations of TBA-PWCu/TBAB and TBA-PWNi/TBAB yielded 60% and 50% conversions, respectively (Fig. 9. (a); comparative ¹H-NMR spectra, Figure S1). Furthermore, when the reaction was monitored over time, as presented in Fig. 9. (b), only 50% conversion was found after 2 hours whereas 60% conversion was observed after 3 hours (¹H-NMR spectra, Figure S2). The conversion of epichlorohydrin was reduced to 60% and 50% when the TBAB loading was reduced to 0.25 mmol and 0.125 mmol, respectively (Fig. 1. (a), Figure S3).

The better catalytic activity of TBA-PWCo catalyst is considered to be due to the higher tendency of cobalt interacting with epoxides [58, 59, and 60]. The morphology of the aggregated particles may make the active sites of the catalyst more accessible and increase the activity. The recyclability studies were performed to emphasize the catalytic capability of TBA-PWCo, and the findings showed that this combined catalytic system can work reasonably well beyond four reuses, as shown in Fig. 10(A). The comparison obtained from ¹H-NMR is shown in Figure S4. Most notably, recyclability investigations show that TBA-PWCo is a highly stable catalyst which can be directly linked to its catalytic performance. The first reuse of the catalyst showed a substantial reduction in catalytic activity, with roughly 17% less production of cyclic carbonate as compared to yield obtained by using the fresh catalyst. Interestingly, for the next three reuses, the catalyst provided the cyclic carbonate with approximately 7% loss in product yield compared to the prior test run while displaying the same level of catalytic activity (Fig. 10 (B), black line; second reuse to fourth reuse). This emphasizes the stability of the catalyst and possible application in industrial operations. Further research can be conducted to improve the performance of catalyst, as there was a 35% decrease in the generation of the product in its fourth reuse when compared with fresh catalyst (Fig. 10 (B), red line).

The reaction conditions used in this article are both practical and economically viable. In order to apply these conditions, 0.12 mol% of TBA-PWCo in combination with TBAB (10 mol %) is used at room temperature in reactions involving structurally different epoxides (Table 1). The cycloaddition of CO₂ to 1, 2-epoxypropane, 1-hexene oxide, 1, 2-epoxycyclopentane, epoxycyclohexane, and styrene oxide progresses under environmentally benign reaction conditions more effectively than previously reported findings (Table 1, entries 1–6). It is interesting to note that octadiene diepoxide formed the symmetrical cyclic dicarbonate effectively, which is encouraging for the potential applications of such intriguing compounds in the future (Table 1, entry 7).

Comparative analysis for the catalytic efficiency of the TBA-PWCo to that of the POM and MOF-based catalysts previously reported for the solvent-free synthesis of cyclic carbonates is shown in Table 2 [37–41]. These catalysts have a better conversion rate than TBA-PWCo but under higher reaction temperature and CO₂ pressure, demonstrating the significantly greater catalytic efficiency of the TBA-PWCo catalyst towards cyclic carbonates. The greater performance of TBA-PWCo is speculated to be induced by oxophillic nature of cobalt towards epoxide [36].

Table 2

Comparative analysis of various catalysts for converting CO₂ into cyclic carbonates
Catalytic system	Temp.(°C)	CO₂ pressure (atm.)	Reaction time (h)	Conversion (%)	Ref.
Zn-POMOF (2 mol%) / TBAB (2.5 mol %)	80	10	12	92	[32]
[Na(H₂O)₅](NH₄)₇P₂W₁₅O₅₆Co₃(H₂O)₃(OH)₃Mn(CO)₃]·19H₂O (0.23 mol%)/ pyrrolidinium bromide (8 mol%)	70	15	1.5	96	[33]
Zn-azatrane complexes a (0.25 mol %) TBAB (0.4 mol%)	110	10	3	79	[61]
V8 Clusters (2 mol%) TBAB (2.5 mol%)	70	5	24	93	[62]
[Co_2.5(LOH)(LO)₂ (H₂O)₂(PW₁₂O₃₉)·3CH₃ CN₂ OH (10 mg)/TBAB (0.16 g)	60	1	4	93	[63]
Na_1.5H_4.5[(CH₃)₄N]₂ [Mn(CO)₃]₄ (Se₂ W₁₁O₄₃)·9H₂O (0.15 mol%)/1-ethyl-1-methylpyrrolidinium bromide (8 mol %)	70	15	1	94.7	[52]
PDDA-PWCo (0.2 mol%) / TBAB (10 mol%)	25	1	3	55	[38]
TBA-PWCo (0.12 mol%) / TBAB (10 mol%)	25	1	4	85	This work

The proposed mechanism for TBA-PWCo/TBAB-catalysed cycloaddition is depicted in Scheme 2. The interaction between TBA-PWCo and oxygen atom activates the oxirane ring which results in nucleophilic oxirane ring opening by TBAB to facilitate a significant increase in reaction rate and product selectivity. As the metal-alkoxide is now exposed, CO₂ insertion occurs which is then followed by intramolecular cyclization and bromide removal to generate cyclic carbonate.

The catalytic process developed in this work requires ambient temperature and solvent-free conditions to produce the desired cyclic carbonates. This convincingly demonstrates that monolacunary catalytic systems substituted with transition metal can produce cyclic carbonates in a way that is environmentally friendly. Furthermore, this catalytic method has the potential to be effective in industrial applications utilizing cyclic carbonates.

Transition metal substituted Keggin type POMs were used as catalysts for the conversion of CO₂ to cyclic carbonates. The synthesized TBA-PWCo, TBA-PWNi, and TBA-PWCu hybrid materials were well characterized establishing the presence of metal substituted Keggin anions with TBA as counter cations. The catalytic performance of these materials in CO₂ conversion to cyclic carbonates was investigated and TBA-PWCo was found to be the most efficient heterogeneous catalyst under environmentally friendly reaction conditions. The cyclic carbonates are produced in high yields with quantitative selectivity, under solvent-free conditions. In addition, the disclosed catalytic technique does not require column purification, minimizing time-consuming operations and waste generation. Moreover, it was observed during the recyclability studies that TBA-PWCo shows around 17% of decrease in its catalytic activity at first reuse, however for next 3 reuses, the catalyst shows only 7% decrease while maintaining the same level of catalytic performance. This highlights the stability of the catalyst and its potential use in flow-reactors or batch-reactors with reusability features. Such catalysts can lead to industrial processes with high turnover number and turnover frequency as these play a key role in industrial scale production. Given all above-mentioned factors, TBA-PWCo-catalysed cyclic carbonate synthesis truly distinguishes itself as a sustainable catalytic approach towards potentially valuable compounds.

Acknowledgement

RJ is greatful to Prof. Ranga Rao for providing research facilites to carry in DSEHC-Solar Fuels Laboratory at IIT Madras. DSEHC is supported by Department of Science and Technology, Government of India through Grant No. DST/TMD/SERI/HUB/1(C). RJ, RRS and KS acknowledge BSACIST for providing chemicals for the synthesis of the catalysts reported here.

Conflicts of interest: The authors have no relevant conflicts of interests to disclose.

Authors' contributions: RJ: material preparation, data collection, early draft and analysis; TKG: data collection and analysis; RRS: study conception; KS: materials design; RRS and KS: study design, monitoring, data analysis, manuscript draft preparation, editing; GRR: study design, monitoring and editing.

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Schemes are available in the Supplementary Files section.

No competing interests reported.

SupplementaryInformation.pdf
Scheme1.png
Scheme 1 Cycloaddition of CO₂ and epichlorohydrin to produce cyclic carbonate
Scheme2.png
Scheme 2 The procedure of employing TBA-TMS-POM catalytic ensembles to cycloaddition, CO₂ to epoxides to synthesize cyclic carbonates

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Sustainable Production of Cyclic Carbonates from CO 2 and Epoxides Using Transition Metal Substituted Polyoxometalate-TBA Hybrid Catalysts

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Abstract

Figures

1. Introduction

2. Experimental

2.1. Materials

2.2 Materials characterization

2.3 Synthesis of hybrid TBA-TMS-POM hybrid materials

3. Results and Discussion

3.1 Physicochemical Characterization

3.2 TBA-TMSPOM catalysed conversion of CO₂ to cyclic carbonates

Conclusion

Declarations

References

Schemes

Additional Declarations

Supplementary Files

Status:

Version 1

Sustainable Production of Cyclic Carbonates from CO 2 and Epoxides Using Transition Metal Substituted Polyoxometalate-TBA Hybrid Catalysts

Status:

Version 1

Abstract

Figures

1. Introduction

2. Experimental

2.1. Materials

2.2 Materials characterization

2.3 Synthesis of hybrid TBA-TMS-POM hybrid materials

3. Results and Discussion

3.1 Physicochemical Characterization

3.2 TBA-TMSPOM catalysed conversion of CO2 to cyclic carbonates

Conclusion

Declarations

References

Schemes

Additional Declarations

Supplementary Files

Status:

Version 1

3.2 TBA-TMSPOM catalysed conversion of CO₂ to cyclic carbonates