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Activation and utilization of CO2 using ionic liquid or amine functionalized basic nanocrystalline zeolites for the synthesis of cyclic carbonates and quinazoline-2,4(1H,3H)-dione Bhaskar Sarmah, and Rajendra Srivastava Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b01406 • Publication Date (Web): 30 Jun 2017 Downloaded from http://pubs.acs.org on July 3, 2017

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Industrial & Engineering Chemistry Research

Activation and utilization of CO2 using ionic liquid or amine functionalized basic nanocrystalline zeolites for the synthesis of cyclic carbonates and quinazoline-2,4(1H,3H)dione

Bhaskar Sarmah and Rajendra Srivastava* Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab-140001, India. E-mail: [email protected] Phone: +91-1881-242175; Fax: +91-1881-223395

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ACS Paragon Plus Environment


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Abstract CO2 was activated and used as a reactant for the preparation of cyclic carbonates and quinazoline-2,4(1H,3H)-dione using functionalized basic nanocrystalline zeolite Nano-ZSM-5 as catalysts. Nano-ZSM-5 was treated with aqueous NH3 solution to prepare basic Nano-ZSM-5. Surface basicity of the basic Nano-ZSM-5 was systematically varied by the surface modification with various amines and basic ionic liquids. Powder X-ray diffraction, N2 adsorption-desorption, scanning/transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy,

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Si and

13

C cross polarized-magic angle spin NMR, elemental analysis,

and temperature programmed desorption techniques were used to characterize the materials. Kinetic (rate constant, activation energy) and thermodynamic parameters (change in enthalpy, free energy, and entropy) were calculated for the cycloaddition reaction of CO2 to epichlorohydrin and 2-aminobenzonitrile by varying the reaction parameters. Basic Nano-ZSM-5 functionalized with methyl imidazolium hydroxide exhibited remarkable high activity and selectivity in the preparation of cyclic carbonates and quinazoline-2,4(1H,3H)-dione. The catalyst was separated and recycled with no significant loss in the activity. In this study mesoporous zeolite was made basic and then the basic property of the nanocrystalline zeolite surface was systemically tuned using various functional amines and ionic liquids under one umbrella.

Keywords: Cycloaddition reaction, CO2 activation, ionic Liquids, basic mesoporous zeolite, functional amines.

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1. Introduction To meet the requirements of human population across the globe, industrial evolution has taken place. Now researchers are developing alternative energy resources based on renewable energy such as fuel from biomass, fuel cell, and so on. The end product of most of these industrial processes, fossil fuel, and biomass-based renewable fuels, enzymatic degradation, and several other such developments is a large concentration of CO2 in the atmosphere.1 This accumulated CO2 imbalances the atmospheric gaseous constituents, especially in the troposphere which is very harmful to the living system on the earth. A large concentration of CO2 in the troposphere is responsible for the global warming.2,3 To sustain earth atmosphere for living being; it is important to balance the CO2 concentration in the atmosphere. Researchers are providing several management plans to take care the CO2 concentration.4 One of the important methods is to convert CO2 into useful chemicals.5-12 Only a few industrial processes based on CO2 are in practice which includes synthesis of urea, salicylic acid, and para-hydroxy benzoic acid, cyclic and polycarbonate, and methanol.12

CO2 is an interesting C1 source material for chemists. Low reactivity of CO2 is due to its kinetic origin as well. Its large accumulation leads to develop an interest to activate and use CO2 in chemical synthesis as useful and renewable feedstock. CO2 is an acidic molecule, and it can be activated catalytically at the metal surface, metal oxide, metal complex and enzyme.13-19 Various modes of CO2 activation have been summarized in one of the reviews.20 Among the various useful chemical processes, reaction of CO2 to epoxide/2-amino benzonitrile for the preparation of cyclic carbonates/quinazoline-2,4(1H,3H)-dione is important because of its atom economy.2131

Cyclic carbonates are important raw materials for the production of engineering plastic,

polycarbonate, and polar aprotic green solvent. Their attractive solvency, negligible toxicity, biodegradability, and high boiling points encourage their applications in dyes, textile, and fibre industry. They are also used as additives in fuel cells, lubricants, and hydraulic fuels. Quinazoline-2,4(1H,3H)-dione acts as a valuable precursor for the synthesis of important medicines.32-33 CO2 based chemical processes has ability to replace conventional commercial synthesis of cyclic carbonate/quinazoline-2,4(1H,3H)-dione which are based on toxic reagents such as potassium cyanate, phosgene, and chlorosulfonyl isocyanate.34-37 3



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CO2 is an acidic molecule, therefore it can be activated by a base catalyst. Metal oxides have been investigated for the synthesis of cyclic carbonate.20 However, a large amount of metal oxide catalyst, non-eco-friendly solvent, and high-pressure condition limits their role in industrial practice. To overcome these limitations, several homogeneous complexes such as porphyrin, phthalocyanine, Schiff’s base, etc. have been investigated.17-19 However, most of these homogenous catalysts require an additional ammonium salt/homogenous base as cocatalyst for the activation of CO2. Efforts have been made to develop titanosilicate based heterogeneous catalyst, but it also requires homogeneous base as co-catalyst for the activation of CO2.38 Furthermore, mesoporous titanosilicate functionalized amine bases have been reported for the preparation of cyclic carbonate.39,40 Catalyst systems based on metal modified SBA-15 and KI have been investigated to catalyze reaction of CO2 to epoxide.42 In recent time, significant efforts have been made to use metal organic framework based catalysts for the synthesis of carbonates.

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Metal organic framework based catalyst alone or in the conjugation with

additive can activate CO2 for cyclic carbonate synthesis.41-45 Heterogeneous pristine carbon nitride and modified carbon nitride are recently being explored for the preparation of cyclic carbonate.46-48 Ionic liquids and tri-s-triazine linked ionic liquids have been recently investigated to use CO2 as a reactant to synthesize cyclic carbonate.50, 51 Similarly, efforts are in progress to develop CO2 based sustainable route for the production of quinazoline-2,4(1H,3H)-dione.34-37, 5152

Zeolites are acid catalysts, therefore it could be difficult to use them in CO2 activation. Synthesis strategy has been developed for the preparation of mesoporous basic zeolite which found to be useful for various base catalyzed organic transformations involving large organic molecules.53 Mesoporous zeolite can be functionalized due to the existence of surface silanol groups. A structured study was carried out by the functionalization of mesoporous basic ZSM-5 zeolite with primary, secondary, and tertiary amines via post-synthesis method. Furthermore, the mesoporus zeolite was also functionalized with quaternary ammonium hydroxide (Brönsted basic ionic liquid). The catalytic activity of parent and functionalized mesoporous basic zeolite was investigated in the transformation of CO2 in the atom-economy production of cyclic carbonate and quinazoline-2,4(1H,3H)-dione.

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2. Experimental section 2.1. Catalyst preparation 2.1.1 Synthesis of Basic-Nano-ZSM-5 Nanocrystalline zeolite (Nano-ZSM-5) (Input Si/Al=20) was synthesized in basic condition (pH ≈ 12) using TPAOH as structure directing agent and n-propyltriethoxysilane as additive by following the reported procedure.54 5 g of calcined sodium-form of zeolite was added to 150 mL of aqueous ammonia (0.2 M) solution and stirred at ambient condition for 4 h. Resultant solid was separated by simple filtration and dried at 323 K for 8 h under vacuum. This process was repeated thrice to get Basic-Nano-ZSM-5.

2.1.2. Amine-functionalized zeolite catalyst The step wise procedure used for the preparation of functionalized materials is provided in Scheme 1. 3-Aminopropyl trimethoxysilane (3 mmol) was added to 30 mL of dry toluene and continuously stirred for 0.5 h at room temperature. Basic-Nano-ZSM-5 (1 g) was added and the suspension was heated at 383 K for 24 h under N2 atmosphere. Solid was filtered and washed with hot toluene several times. It was then dried under vacuum at 353 K for 8 h. The material is named as Basic-Nano-ZSM-5-Pr-NH2. The step wise procedure used to synthesize other amine functionalized Basic-Nano-ZSM5 catalyst is shown in Scheme 1. Synthetic steps shown in Scheme 1 are fairly known in the literature.55 Basic-Nano-ZSM-5 (2 g) was reacted with 3-chloropropyltriethoxysilane (6 mmol) in 40 mL dry toluene at 393 K for 24 h. Solid was filtered and washed with hot toluene several times. It was then dried under vacuum at 353 K for 8 h, and the resultant material is named as Basic-Nano-ZSM-5-Pr-Cl. Then, Basic-Nano-ZSM-5-Pr-Cl (1 g) was reacted with different amines (di-propyl amine and butyl amine) in the presence of NaH (amine:NaH = 1 mmol : 1.5 mmol) in 30 mL dry THF under N2 environment at 273 K for 1 h. Then it was heated at 343 K for 16 h. Resultant solid was filtered and thoroughly washed, first with THF, and then with ethanol. It was then dried in vacuum for 8 h at 353 K. Materials prepared with di-propyl amine and butylamine are named as Nano-ZSM-5-Pr-DPA and Nano-ZSM-5-Pr-BuA, respectively. 5



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2.1.3. Preparation of ionic liquids functionalized Basic-Nano-ZSM-5 The schematic presentation of the synthetic route followed in the preparation of functionalized ionic liquids (ILs) is presented in Scheme 1. In a 100 mL double necked flask, Nmethyl imidazole (10 mmol) and 30 ml dry toluene were taken. 3-chloropropyltriethoxy silane (10 mmol) was slowly added in 10 min. It was then refluxed for 1 day in N2 environment under stirring condition. After the reaction, toluene was evaporated. Resultant material was treated several times with diethyl ether to remove any un-reacted reactants. Finally, the material was dried in vacuum at 353 K to get chloropropyl silylated imidazolium chloride. 3 mmol of chloropropyl silylated imidazolium chloride and 30 mL of dry toluene were taken in a flask and then Basic-Nano-ZSM-5 (1 g) was added. The flask was heated at 383 K for 1 d in N2 environment. It was then cooled to room temperature and filtered using Whatman filter paper. Solid was first washed with toluene and then with a hot mixture of ether and dichloromethane (1:1) to remove excess ILs. Finally, it was dried in vacuum at 353 K for 12 h to obtain BasicNano-ZSM-5-Pr-MIM-Cl. NMR data for (chloropropyl silylated imidazolium chloride): 1H NMR (400 MHz, CDCl3): δ 10.72 (s, 1H), 7.33 (s, 1H), 7.25 (s, 1H), 4.32 (t, 2H), 4.10 (s, 3H), 3.81-3.76 (q, 6H), 2.02-1.94 (m, 2H), 1.20-1.17 (t, 9H), 0.60-0.56 (t, 2H);

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C NMR (100 MHz, CDCl3): δ 138.7, 123.0,

121.7, 58.8, 52.0, 36.8, 24.5, 18.4, 7.3

For

the

preparation

of

DMAP

based

ILs,

first

1-triethoxysilylpropyl-4-

dimethylpyridinium chloride was prepared. N, N-dimethylamino pyridine (10 mmol) and 20 mL acetone were taken in a double necked flask. 3-chloropropyltriethoxysilane (10.1 mmol) was added slowly in 10 min. The flask was heated at 333 K for 1 day in N2 environment under constant stirring. Acetone was evaporated and the white residue was treated with acetone 3-5 times. The resultant material was dried in vacuum at 333 K to get 1-triethoxysilylpropyl-4dimethylpyridinium chloride. 1-triethoxysilylpropyl-4-dimethylpyridinium chloride (3 mmol) was added to 30 mL of toluene/methanol (80:20) containing 1 g of Basic-Nano-ZSM-5. The reaction mixture was heated at 353 K for 1 d in N2 atmosphere under constant stirring. The flask 6


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was cooled to room temperature. Solid was filtered and washed several times with methanol. Finally, it was dried in vacuum at 353 K for 8 h to get Basic-Nano-ZSM-5-Pr-DMAP-Cl. NMR data for (1-triethoxysilylpropyl-4-dimethylpyridinium chloride): 1H NMR (400 MHz, D2O): δ 7.97–7.95 (m, 2H), 6.85-6.81 (m, 2H), 4.79-4.75 (t, 2H), 3.10-3.15 (q, 6H), 3.05 (s, 6H), 1.80-1.76 (m, 2H), 1.18-1.14 (t, 9H), 0.56-0.51 (t, 2H);

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C NMR (100 MHz, D2O): δ 141.3,

156.3, 107.5, 61.4, 59.6, 39.3, 24.2, 19.8, 8.9.

For the preparation of 1,4-diazabicyclo[2.2.2]octane (DABCO) based ILs, first 1triethoxysilylpropyl DABCO chloride was prepared. 5 mmol DABCO and 5.05 mmol 3chloropropyltriethoxysilane were mixed with 10 mL DMF and stirred at 373 K for 2 d. The solvent was evaporated under reduced pressure; viscous jelly-like product was obtained. 3 mmol of 1-triethoxysilylpropyl DABCO chloride was added to 30 mL of toluene/methanol (80:20) containing 1 g of Basic-Nano-ZSM-5. Flask was heated at 353 K for 1 d in N2 atmosphere under constant stirring. The flask was cooled to room temperature. Solid was filtered and washed several times with methanol. Finally, it was dried in vacuum at 353 K for 8 h to get Basic-NanoZSM-5-Pr-DABCO-Cl. NMR data for (1-triethoxysilylpropyl DABCO chloride): 1H NMR (400 MHz, D2O): δ 3.85– 3.82 (m, 3H), 3.59-3.53 (m, 3H), 3.34-3.30 (m, 6H), 3.21-3.19 (t, 2H), 3.13-3.09 (q, 6H), 1.831.74 (m, 2H), 1.16-1.10 (t, 9H), 0.61-0.56 (t, 2H); 13C NMR (100 MHz, D2O): δ 66.3, 60.4, 52.1, 50.5, 17.8, 14.7, 8.3. 1 g of Basic-Nano-ZSM-5-Pr-MIM-Cl/Basic-Nano-ZSM-5-Pr-DMAP-Cl/Basic-NanoZSM-5-Pr-DABCO-Cl was treated with 0.2 M methanol solution of TMAOH (25% in methanol, using liquid/solid mass ratio of 50) at room temperature for 4 h. Solid was filtered and washed several times with methanol. Finally, it was dried in vacuum at 353 K for 6 h. Obtained materials are named as Basic-Nano-ZSM-5-Pr-MIM-OH/Basic-Nano-ZSM-5-Pr-DMAP-OH/Basic-NanoZSM-5-Pr-DABCO-OH. 1 g of Basic-Nano-ZSM-5-Pr-MIM-Cl was treated with 50 mL of 0.4 M aqueous solution of KHCO3 at room temperature for 1 d. Solid was filtered and washed several times with water. 7



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Finally, it was dried in vacuum at 353 K for 1 d. Obtained material is named as Basic-NanoZSM-5-Pr-MIM-HCO3.

2.2. Catalytic reactions 2.2.1 Cycloaddition of CO2 with epoxides Cycloaddition reaction was conducted in a Paar autoclave (stainless steel) fitted with a mechanical stirrer. Epichlorohydrin (51 mmol, 4 mL) and catalyst (50 mg) were taken into the autoclave. The autoclave was purged with CO2 and then pressurized to 8 bar. The autoclave was heated at 393 K for 4 h under stirring condition (1000 rpm). After the reaction, it was cooled to room temperature and the reaction mixture was diluted with dichloromethane. Catalyst was sepereated using centrifuge machine. The reaction mixture was analyzed by GC (Yonglin 6100; BP-5; 30 m × 0.25 mm × 0.25 µm) and product was confirmed using GC-MS (Schimadzu GCMS-QP 2010 Ultra; Rtx-5 Sil Ms; 30 m × 0.25 mm × 0.25 µm).

2.2.2 Synthesis of quinazoline-2,4(1H,3H)-diones 2-aminobenzonitrile (2 mmol), DMF (10 mL), and catalyst (100 mg) were placed in a Paar autoclave fitted with a mechanical stirrer. The autoclave was purged with CO2 and then pressurized to 35 bar. The autoclave was heated at 423 K for 12 h. It was cooled to room temperature, and the catalyst was separated using centrifuge machine. Reaction mixture was added to a flask which contained the crushed ice. The flask was kept in refrigerator for 10-12 h for the precipitation of the product. Precipitated solid was filtered and thoroughly washed with cold water. Finally solid was dried in vacuum for 8-10 h. Product was confirmed using 1H NMR and FT-IR that matched well with the reported literature.56

3. Results and discussion 3.1. Catalyst characterization XRD pattern of Nano-ZSM-5 matched with MFI framework structure (Figure 1a).54 Nano-ZSM-5 exhibited broad XRD pattern when compared to conventional ZSM-5,54 which shows the nanocrystalline nature of the material. Basic-Nano-ZSM-5 exhibited similar XRD pattern to that of Nano-ZSM-5. However, the XRD peak intensity of Basic-Nano-ZSM-5 was 8


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reduced when compared to Nano-ZSM-5, which is due to the partial collapse of the crystalline framework of the ZSM-5 framework after the aqueous NH3 treatment. XRD patterns of various base functionalized materials are shown in Figure 1b and Figure 1c. XRD patterns show that the framework structure of the parent material was not altered after the base functionalization. However, the peak intensity of parent Basic-Nano-ZSM-5 was somewhat reduced after the functionalization of bases on its surface.

N2-adsorption-desorption measurement was carried out to estimate the textural properties of the material. Type-IV isotherm was obtained for Nano-ZSM-5 during N2-adsorption investigation (Figure 2). Capillary condensation in the inter-crystalline mesopore void spaces took place which is confirmed from the increase of N2 adsorption in the region 0.4 primary amine (Basic-Nano-ZSM-5-Pr-NH2). ILs functionalized catalysts exhibited more activity than that of amine functionalized bases. The order of activity follows the following trend: Basic-Nano-ZSM-5-Pr-MIM-Cl>Basic-Nano-ZSM-5-Pr-DMAP12


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Cl>Basic-Nano-ZSM-5-Pr-DABCO-Cl. Chloride ion was replaced with HCO3- and OH- to prepare basic ILs. Catalytic activity data shows that OH- based ILs exhibited the best activity. The order of reactivity follows the following trend: OH- > HCO3- > Cl-. Results demonstrate that Basic-Nano-ZSM-5-Pr-MIM-OH exhibited the best activity for the cycloaddition of CO2 to ECH. High activity of Basic-Nano-ZSM-5-Pr-MIM-OH agreed with the basicity and textural properties of the material. Surface silanol groups and external surface area were responsible for the tethering of highly dispersed surface functionalized Pr-MIM-OH groups that exhibited higher basicity than other ILs (based on TPD results). The simultaneous participation of surface silanol groups and high basicity of the Basic-Nano-ZSM-5-Pr-MIM-OH are accountable for the excellent activity in the cycloaddition reaction of CO2 to ECH. Having found the best catalyst for the cycloaddition reaction, reaction parameters were optimized. Cyclic carbonate yield was influenced by the CO2 pressure (Figure 9a). ECH conversion was increased with increase in the CO2 pressure. At low pressures (2 bar), the ECH conversion was close to 30 %. But at 8 bar, the conversion was >90%. No appreciable increase in the ECH conversion was noticed above this pressure. It is kept in mind that the reaction parameters were optimized in neat condition. Dissolved CO2 molecules at the optimum pressure range can act as diluents to facilitate the reaction. Here catalyst rich solid phase is sandwiched with bottom ECH rich liquid phase and the top CO2 rich gas phase. At pressure lower than 8 bar, CO2 was compressed and present in the liquid phase which improved the cyclic carbonate yield. At the optimum reaction temperature and pressure higher than 8 bar, ECH could be present in the gaseous form, which could decrease the concentration of ECH at the interface and therefore no further improvement in the yield was observed. Influence of CO2 pressure leads to provide following conclusion: (1) CO2 should not be considered in the rate expression; (2) in this pressure range, CO2 activation is determined by the nature of the functional groups tethered to the surface of Basic-Nano-ZSM-5; (3) good solubility of CO2 in the reaction medium at optimum pressure range.

Influence of catalyst amount was investigated (Figure 9b). ECH conversion was increased up to 50 mg of catalyst. Above this amount, no appreciable increase in the ECH 13



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conversion was obtained. This provides evidence that at the optimum reaction condition, the optimum numbers of reactive species were generated using 50 mg of catalyst with adsorbed CO2 which could react with ECH present in the vicinity to provide the highest activity. Beyond this amount, more numbers of CO2 activated species could have been formed but it would have not been converted to product due to the unavailability of reactive partners (ECH) in the volume domain of the investigation. Therefore, 50 mg of catalyst was selected as optimum catalyst amount for further investigation. Figure 9c shows that the temperature exhibits remarkable influence on the epoxide conversion. With the increase in the temperature, epoxide conversion was increased. At low temperatures (353 K), the conversion of epoxide was only 10.7 %, whereas it reached to 90.1% at 393 K indicating that most of the ECH molecules attained the required activation energy for this reaction at 393 K. No significant increase in the ECH conversion was observed above 393 K, demonstrating that 393 K was ideal for this reaction. At higher temperature, ECH could be present in the gas phase, which resulted the decrease in the concentration of ECH at the CO2-catalyst interface and therefore no significant improvement in the ECH conversion was observed at temperature higher than 393 K. Another important feature of this reaction is that with an increase in temperature, cyclic carbonate selectivity was improved. Influence of reaction time showed that a reaction time of 4 h was optimum to achieve high cyclic carbonate yield. With increase in the reaction time, increase in the CO2 consumption took place to form cyclic carbonate, which resulted reduction in the CO2 pressure in the reaction vessel. After 4 h of the reaction, significant fraction of CO2 was consumed, therefore, optimum pressure was not maintained after 4 h of the reaction which could be responsible for no appreciable increase in the epoxide conversion.

Other aliphatic and aromatic epoxides were investigated to synthesize the corresponding cyclic carbonate under optimum reaction condition over the best catalyst Basic-Nano-ZSM-5-PrMIM-OH and the results are presented in Table 2. Among the three epoxides investigated in this study, epichlorohydrin exhibited the highest activity in four hours (Table 2). Good styrene oxide conversion was obtained when the reaction was conducted for longer duration (Table 2). The recyclability of the catalyst was examined under the optimum condition. After the reaction, the catalyst was recovered using centrifuge machine, rinsed with dichloromethane and dried in an 14


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oven for 4 h at 353 K. Then the recovered catalyst was used in the next cycle. Basic-Nano-ZSM5-Pr-MIM-OH was recycled and the results are shown in Figure S2. Recycling experiments show that the ECH conversion and cyclic carbonate selectivity were consistent during the five recycles. These results strongly suggest that the present catalyst can be used multiple times for carbonate synthesis. Recovered catalyst was subjected to XRD, BET, TGA, and TPD analysis. XRD pattern shows that no change in the framework structure was observed (Figure S3). No appreciable change in the surface area and pore volume was obtained for the recovered catalyst when compared to the fresh catalyst (Table 1). TGA analysis showed that 10.22 wt% of loss occurred for the recycled catalyst (TGA loss for the fresh catalyst was 10.57 wt%) (Figure S4). FT-IR spectrum of the recovered catalyst shows that the organic groups were retained on the surface even after it was recycled for five times in the catalytic test (Figure S5). TPD profiles of fresh and recovered catalysts were similar which confirms that basicity was not lost during the recycling study (Figure S6). Based on these characterizations, one can conclude that no appreciable change in the framework structure and functionalization took place when the catalyst was recycled for five times. Reaction with five times higher charge [(ECH (255 mmol) and catalyst (250 mg)] was also performed. 6 h was required to achieve similar conversion (ECH conversion = 93.8 ± 1.2 %) and selectivity (96.4 ± 0.3 %) to that of less charge value (ECH = 51 mmol).

Kinetic of cycloaddition was studied using ECH. The general rate formula for cycloaddition is given by Eq. (1). Rate = dx/dt = k (ECH)a(CO2)b(Catalyst)c ------------------- (1) Under the optimum reaction condition, a large excess of CO2 was taken therefore CO2 concentration was kept constant. Furthermore, catalyst amount was also kept constant under the present investigation for the kinetic investigation; therefore Eq. (1) can be simplified to Eq. (2). Rate = dx/dt = kobs (ECH)a ------------------- (2) Where kobs is the observed rate constant of the current study. 15



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Cycloaddition reactions were carried out at 393 K by varying the ECH concentration from 51 mmol-204 mmol, while keeping CO2 pressure and catalyst amount constant. With increase in the ECH concentration, ECH conversion was decreased. The rate was plotted versus ECH concentration (Figure 9e). Rate of cycloaddition reaction shows a 1st order dependence with respect to the ECH concentration. Therefore, Eq. (2) can be reduced to Eq. (4).

-ln [ECH] = kobs t

------------- (3)

Rate = kobs (ECH)1

------------- (4)

kobs = A exp (-Ea/RT) ------------- (5) ln kobs = ln A –Ea/RT

------------- (6)

From the Arrhenius plot of ln kobs versus 1/T shown in Figure 10a in the temperature range of 333–393 K, the activation energy Ea was calculated (Where R (8.314 Jmol-1 K-1), T (in K) and A have standard meaning). From the Arrhenius plot, the activation enthalpy (∆H = EaRT) was determined. Further, using the expression ∆G = -RT ln (NAhk/RT), the free energy of activation (∆G) was calculated at 393 K;63 where R, NA, h, k have their standard meaning. Activation of entropy (∆S) was calculated using expression ∆S = (∆H - ∆G)/T. The values of Ea, ∆H, ∆G, and ∆S were calculated to be 59.24 kJ mol−1, 55.97 kJ mol−1, 40.94 kJ mol−1, and 0.125 kJ mol−1 °C−1, respectively.

A plausible mechanism for the reaction between epoxide and CO2 is shown in Scheme S1. A synergistic participation of bi-functional sites present in the catalyst was responsible for the high catalytic activity. Simultaneous activation of CO2 with amines/ILs and epoxide ring with surface silanol groups took place. Oxygen anion of the epoxide reacted with the C=O group of the activated CO2 through intramolecular nucleophilic cyclization to form cyclic carbonate. Having found the best catalyst for the cycloaddition reaction, the applicability of BasicNano-ZSM-5-Pr-MIM-OH was investigated in the synthesis of quinazoline-2,4(1H,3H)-dione by the reaction of 2-aminobenzonitrile and CO2. Influence of the reaction parameters was studied to 16


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optimize the reaction condition. In this case, only one product, quinazoline-2,4(1H,3H)-dione was obtained. First influence of solvent was investigated (Table 3). In contrast to the above reaction, this reaction did not proceed in solvent free condition. It was found that reaction proceeded well in DMF or DMSO. The reaction did not take place in the non-polar solvents such as toluene (Table 3). The reaction did not take place in the aprotic polar solvent acetonitrile whereas only a low product yield was obtained in a polar protic solvent, methanol (Table 3). Further, H2O as a reaction medium afforded moderate product yield (Table 3). Easy recovery and high yield of the product in DMF encouraged us to choose this solvent for further investigation.

Quinazoline-2,4(1H,3H)-dione yield was influenced by the CO2 pressure and the results are shown in Table 3. At a lower pressure of 20 bar, the product yield was low (48.7%). But as the pressure was increased to 35 bar, the product yield was increased to 93.6%. A further increase in the CO2 pressure did not influence the product yield (Table 3). In this case also CO2 should not be considered in the rate determining step due to their large concentration at the experimental condition when compared to reactant 2-aminobenzonitrile concentration. Influence of catalyst amount shows that 100 mg of the catalyst was optimum for this reaction (Table 3). Table 3 shows that temperature exhibited a remarkable influence on the 2aminobenzonitrile conversion. With the increase in the temperature, 2-aminobenzonitrile conversion was increased. At lower temperatures (373 K), no reaction took place. The conversion of 2-aminobenzonitrile was less than 30% when the temperature was 393 K whereas it reached to 93.6 % at 423 K, which suggests that most of the reactant molecules attained the required activation energy for the reaction. No appreciable increase in the activity was observed above 423 K, demonstrating that 423 K was ideal temperature for this reaction. Influence of reaction time was investigated at 423 K and 35 bar. 2aminobenzonitrile conversion increased from 4 h to 12 h and then remained almost constant with increases in the reaction time. Therefore, 12 h was required to obtain the high yield of product.

Kinetic of cycloaddition was studied using 2-aminobenzonitrile. The general rate formula for cycloaddition is given by Eq. (7).

17



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Page 18 of 46

Rate = dx/dt = k (2-amino benzonitrile)a(CO2)b(Cat)c ------------------- (7) Similar to the above reaction, this reaction was 1st order with respect to the 2aminobenzonitrile concentration. As considered in the case of cycloaddition of CO2 to epoxide in this case also the rate expression can be written as Rate = dx/dt = kobs (2-aminobenzonitrile)1 ------------------- (8) Eq. (8) can be expressed as Eq (9) given below. Rate = kobs (2-aminobenzonitrile)1

------------- (9)

From the Arrhenius plot of ln kobs versus 1/T shown in Figure 10b, the activation energy Ea was calculated. Using the various thermodynamic expressions defined above, the values of Ea, ∆H, ∆G, and ∆S were calculated to be 58.6 kJ mol−1, 55.04 kJ mol−1, 52.77 kJ mol−1, and 0.015 kJ mol−1 °C−1, respectively.

In this case, basic sites of the catalyst activate CO2 molecule and also abstract an acidic proton from NH2 group of 2-aminobenzonitrile due to the electron withdrawing group (-CN) attached to the benzene ring leading to the formation of intermediate 1a (Scheme S2). In the second step, intermediate 1a undergoes nucleophilic attack to CO2 molecule, thereby generates intermediate 1b. Then, oxygen anion in the intermediate 1b attacks the –CN group and generates cyclic intermediate 1c. Ring opening of intermediate 1c leads to form isocyanate intermediate 1d which undergoes intramolecular cyclization leading to form intermediate 1e. Tautomerization of 1e leads to form stable cyclic amide quinazoline-2,4(1H,3H)-dione product and regenerates the catalyst.

4. Conclusions Activation and utilization of CO2 for the production of cyclic carbonate and quinazoline2,4(1H,3H)-dione over Basic-Nano-ZSM-5 functionalized with amines (primary, secondary and tertiary amines) and ionic liquids (based on imidazole, DABCO, and DMAP) were successfully demonstrated. Organic bases were tethered on the surface of Basic-Nano-ZSM-5 through propyl 18


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spacer.

29

Si &

13

C CP-MAS NMR, FT-IR and TGA analysis confirmed the incorporation of

functionalized bases and ionic liquids. Basicity of the materials was quantified using CO2-TPD. The imidazolium hydroxide-functionalized Basic-Nano-ZSM-5 offered the highest activity for the synthesis of cyclic carbonate in the absence of solvent or co-catalyst/promoter. High activity correlated well with the basicity of the catalyst obtained from TPD investigation. Application of the highly active catalyst was successfully demonstrated in the synthesis of quinazoline2,4(1H,3H)-dione. Activation energy for the reaction between CO2 & epichlorohydrin and CO2 & 2-aminobenzonitrile were calculated to be 58.6 kJ mol−1 and 59.24 kJ mol−1, respectively. Simultaneous activation of CO2 and epoxide/2-aminobenzonitrile by the synergistic participation of bi-functional sites present in the catalyst was key to achieve the high catalytic activity with imidazolium hydroxide-functionalized Basic-Nano-ZSM-5. Supporting Information Details of materials and catalyst characterization techniques have been provided. EDAX spectra of Basic-Nano-ZSM-5-Pr-DMAP-OH and Basic-Nano-ZSM-5-Pr-MIM-OH (Figure S1) and recycling data obtained during the reaction between CO2 and epichlorohydrin using Basic-NanoZSM-5-Pr-MIM-OH (Figure S2) is provided in supporting information. XRD, TGA, FT-IR, and TPD of recycled catalyst are presented in Figure S3-S6. Plausible mechanism for the synthesis of cyclic carbonate and quinazoline-2,4(1H,3H)-dione are shown in Scheme S1 and Scheme 2.

Acknowledgement Authors acknowledge CSIR, New Delhi for funding (01/(2802)/14/EMR-II). BS acknowledges UGC, New Delhi for SRF fellowship. Authors are grateful to Director, IIT Ropar for funding TPD instrument through interdisciplinary programme on energy. Authors acknowledge the support received from SAIF, IIT Bombay for HRTEM analysis and Dr. Ajith Kumar, National Chemical Laboratory, Pune for 29Si & 13C CP-MAS NMR analysis.

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Table, Figure, and Scheme caption

Table Table 1.

Textural properties of parent and selected functionalized catalysts investigated in this study.

Table 2.

Amount of organic groups present in various catalysts obtained using TGA and CHN analysis.

Table 3.

Influence of catalyst and epoxide in the synthesis of cyclic carbonates.

Table 4.

Influence of reaction parameters in the synthesis of quinazoline-2,4(1H,3H)-dione.

Figure Figure 1.

XRD patterns of zeolite materials investigated in this study.

Figure 2.

N2 adsorption-desorption isotherms of Nano-ZSM-5, Basic-Nano-ZSM-5 and selected functionalized Basic-Nano-ZSM-5 investigated in this study (inset shows pore size distribution).

Figure 3.

SEM

micrographs

of

Nano-ZSM-5,

Basic-Nano-ZSM-5

and

selected

functionalized Basic-Nano-ZSM-5 investigated in this study. Figure 4.

TEM images of Nano-ZSM-5 and Basic-Nano-ZSM-5-Pr-MIM-OH

Figure 5.

FT-IR spectra of various functionalized Basic-Nano-ZSM-5 investigated in this study.

Figure 6.

(a)

29

Si and (b)

13

C CP-MAS NMR spectra of Basic-Nano-ZSM-5-Pr-MIM-

OH. Figure 7.

Thermograms of various functionalized Basic-Nano-ZSM-5 investigated in this study.

Figure 8.

CO2-TPD profiles of Basic-Nano-ZSM-5 and OH containing ILs functionalized Basic-Nano-ZSM-5 catalysts investigated in this study.

Figure 9.

Influence of reaction parameters such as (a) CO2 pressure, (b) catalyst amount, (c) temperature, (d) time, and (e) epichlorohydrin concentration in the cycloaddition reaction of CO2 to epichlorohydrin over Basic-Nano-ZSM-5-PrMIM-OH. 27



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Figure 10.

Plot for ln kobs vs 1/T for the calculation of activation energy for the cycloaddition reaction of (a) CO2 to epoxide and (b) CO2 to 2aminobenzonitrile.

Scheme Scheme 1

Synthetic protocols adopted for the preparation of amines/ionic liquids functionalized catalysts prepared in this study.

28


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Table1. Textural properties of parent and selected functionalized catalysts investigated in this study. Materials

Surface area External 2 -1

SBET (m g )

surface

Total

Mesopore 3 -1

area volume (cm g )

(m2g-1)

volume (cm3g-1)

Nano-ZSM-5

554

312

0.39

0.56

Basic-Nano-ZSM-5

404

202

0.26

0.38

Basic-Nano-ZSM-5-Pr-

345

148

0.17

0.32

336

140

0.18

0.31

338

142

0.18

0.31

MIM-OH Basic-Nano-ZSM-5-PrDMAP-OH Basic-Nano-ZSM-5-PrMIM-OHa a

Recovered catalyst.

29


pore


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Page 30 of 46

Table 2. Amount of organic groups present in various catalysts obtained using TGA and CHN analysis. Catalyst

Amount of functionalized organic moiety (mmol/g) Based on TGA

Based on CHN

Basic-Nano-ZSM-5-Pr-MIM-OH

0.75

0.72

Basic-Nano-ZSM-5-Pr-DMAP-OH

0.95

0.92

Basic-Nano-ZSM-5-Pr-DABCO-OH

0.77

0.73

Basic-Nano-ZSM-5-Pr-NH2

2.1

2.02

Basic-Nano-ZSM-5-Pr-BuA

0.77

0.75

Basic-Nano-ZSM-5-Pr-DPA

0.88

0.85

30


Page 31 of 46

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Table 3. Influence of catalyst and epoxide in the synthesis of cyclic carbonates.

E. N a

1

Catalyst

Nano-ZSM-5

Reactant

Time (h) 4

Conv. (%)

Product select. (%)

0.6

TOF (h-1)

-

(78.0) b

2

Basic-Nano-ZSM-5

4

-

7.2

(83.8 ) 3

Basic-Nano-ZSM-5Pr-NH2

4

13.8

11.4 ± 0.5

(85.8 ± 0.3) 4.

Basic-Nano-ZSM-5Pr-BuA

4

122.8

36.9 ± 0.7

(95.8 ± 0.6) 5.

Basic-Nano-ZSM-5Pr-DPA

4

129.2

44.7 ± 1.0

(96.6 ± 0.4) 6

Basic-Nano-ZSM-5Pr-MIM-Cl

4

248.2

72.6 ± 1.2

(96.9 ± 0.7) 7

Basic-Nano-ZSM-5Pr-DABCO-Cl

4

65.2 ± 0.8

31


217.0


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 46

(96.4 ± 0.2) 8.

Basic-Nano-ZSM-5Pr-DMAP-Cl

4

228.3

85.4 ± 1.3

(95.2 ± 0.6) 9.

Basic-Nano-ZSM-5Pr-MIM-HCO3

4

267.0

78.1 ± 1.1

(95.5 ± 0.5) 10

Basic-Nano-ZSM-5Pr-MIM-OH

4

307.8

90.1 ± 0.9

(97.1 ± 0.3) 11

Basic-Nano-ZSM-5Pr-DABCO-OH

4

234.6

70.5 ± 1.2

(96.4 ± 0.7) 12

Basic-Nano-ZSM-5Pr-DMAP-OH

4

257.2

96.2 ± 1.4

(95.7 ± 0.4) 13.


4

302.3

88.5 ± 1.0

(99.6 ± 0.4 ) 14


4

104.2

30.5 ± 0.6

(96.8 ± 0.7) 15


12

92.0

80.8 ± 0.9

(97.2 ± 0.4)

32


Page 33 of 46

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Reaction condition: Epoxide (51 mmol), catalyst (50 mg), time (4 h), CO2 (8 bar), temperature (393 K). a,b Data denotes reaction carried out using 100 mg catalyst. Side products obtained during the insertion reaction of CO2 to epichlorohydrin = or Side products obtained during the insertion reaction of CO2 to styrene oxide = Values in the entry nos. 3-15 are presented as mean ± SD (n = 3); SD = standard deviation.

33



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 46

Table 4. Influence of reaction parameters in the synthesis of quinazoline-2,4(1H,3H)-dione.

E.N

Solvent

Temp.

Pressure

Catalyst

Product

(K)

(Bar)

amount

yield. (%)

(mg) 1

DMF

423 K

35

100 mg

93.6 ± 0.5

2.

DMSO

423 K

35

100 mg

94.2 ± 0.9

3.

Water

423 K

35

100 mg

42.4 ± 0.4

4.

Methanol

423 K

35

100 mg

6.7 ± 0.6

5.

Acetonitrile

423 K

35

100 mg

0

6.

Toluene

423 K

35

100 mg

0

8.

Neat

423 K

35

100 mg

0

9

DMF

423 K

20

100 mg

48.7 ± 0.5

10

DMF

423 K

30

100 mg

75.4 ± 0.7

11

DMF

423 K

40

100 mg

96.1 ± 0.3

12

DMF

423 K

35

25 mg

30.6 ± 0.4

13

DMF

423 K

35

50 mg

53.8 ± 0.6

14

DMF

423 K

35

125 mg

96.7 ± 0.2

15

DMF

393 K

35

100 mg

26.4± 0.3

16

DMF

403 K

35

100 mg

42.4 ± 0.5

17

DMF

413 K

35

100 mg

64.5 ± 0.7

Reaction conditions: 2-aminobenzonitrile (2 mmol), solvent (10 mL), catalyst (100 mg), time (12 h), temperature (423 K), CO2 (35 bar). Values are presented as mean ± SD (n = 3); SD = standard deviation.

34


Page 35 of 46

200 600

100

Basic-Nano-ZSM-5-Pr-DPA

50 Basic Nano-ZSM-5

200

0 10

20

30

40

50

60

70

Intensity (a.u.)

400

2000

(b)

150

(a)

Intensity (a.u.)

80

0 10

200 1000

20

30

40

250 200 150 100 50 0

1500

50

60

70

80

Basic-Nano-ZSM-5-Pr-BuA

10

20

30

40

50

60

70

80

150

Nano-ZSM-5

Basic-Nano-ZSM-5-Pr-NH2

100 500

50 0

0 10

20

30

40

50

60

70

10

80

20

30

40

50

60

70

80

2θ (Degree)

2θ (Degree) 400

(c)

300

Basic-Nano-ZSM-5-Pr-DABCO-OH

200 100 0

Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


10

20

30

40

50

60

70

80

300 200

Basic-Nano-ZSM-5-Pr-DMAP-OH

100 0 300

10

20

200

30

40

50

60

70

80

Basic-Nano-ZSM-5-Pr-MIM-OH

100 0 10

20

30

40

50

60

70

80

2θ (Degree) Figure 1 35



350

1.0

250

0.8

-1

-1

dV/dD (mLg nm )

300

Adsorbed amount (mL/g)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 46

200

0.6 0.4 0.2 0.0

0 5 10 15 20 25 30 Pore diameter (nm)

150 100 50 0 0.0

Nano-ZSM-5 Basic-Nano-ZSM-5 Basic-Nano-ZSM-5-Pr-DMAP-OH Basic-Nano-ZSM-5-Pr-MIM-OH

0.2

0.4

0.6

0.8

1.0

Relative pressure (P/P 0) Figure 2

36


Page 37 of 46

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 3

37



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 38 of 46

Figure 4

38


4000

3500

3000

2500

2000

1500

1000

Zeolite framework

Symm. Si -O- Si

Basic-Nano-ZSM-5 Basic-Nano-ZSM-5-pr-NH2 Basic-Nano-ZSM-5-pr-MIM-OH Basic-Nano-ZSM-5-pr-DMAP-OH Basic-Nano-ZSM-5-pr-DABCO-OH

............................ C-N Stretch. or Asymm. Si -O -Si

-C=C Stretch. -C=N Stretch. -CH2 Bending

-NH Bending

2

H . Asymm. -CH2 Sy m m .C

ch et tr -S H -N

.......................... -OH Stretch.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


% Transmittance (a.u.)

Page 39 of 46

500

-1

Wavenumber (cm ) Figure 5

39



..........

Q4

50

0

-50

..........

T3

100

(a)

Q3

T2 .......... ..........

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 40 of 46

-100

-150

-200

-250

Chemical shift (ppm) (b)

b g&f h d c e

i a

250

200

150

100

50

0

-50

-100

Chemical shift (ppm) Figure 6 40


(a)

100

95

Weight (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


90

10.57

85 13.14

80

17.32

Basic-Nano-ZSM-5 Basic-Nano-ZSM-5-Pr-DABCO-OH Basic-Nano-ZSM-5-Pr-DMAP-OH Basic-Nano-ZSM-5-Pr-MIM-OH

75 400

600

800

1000

1200

Temperature (K)

(b) 100

95

Weight (%)

Page 41 of 46

90

8.75

85

12.55 12.22

Basic-Nano-ZSM-5 Basic-Nano-ZSM-5-Pr-NH2 Basic-Nano-ZSM-5-Pr-BuA Basic-Nano-ZSM-5-Pr-DPA

80

400

600

800

1000

1200

Temperature (K) Figure 7 41



700

Basic-Nano-ZSM-5 Basic-Nano-ZSM-5-pr-MIM-OH Basic-Nano-ZSM-5-pr-DABCO-OH Basic-Nano-ZSM-5-pr-DMAP-OH

600

TCD Signal (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 42 of 46

500 400 300 200 100 0 350

400

450

500

550

Temperature (K) Figure 8

42


Page 43 of 46

100

100

(a)

80 70 60 50 40 30 20 10

Epichlorohydrin conv. (%) Cyclic carbonate select. (%) 4

6

8

80

(b) 70 60 50 40 30 20 10

0

Epichlorohydrin conv. (%) Cyclic carbonate select. (%)

0

10

0

CO2 pressure (Bar)

10

20

30

40

50

60

70

90

(c)

80 70 60 50 40 30 20 10


0

350 360 370 380 390 400 410

Catalyst amount (mg)

Temperature (K)

20 100

19

90

(d)

80

Rate (10 M/min)

70 60

(e)

18

17

-5

2

90

Conversion and selectivity (%)

90


100



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


50 40 30 20

16

15

14

10


13

0 0

1

2

3

4

5

6

Time (h)

50

100

150

200 -3

Epichlorohydrin (10 M)

Figure 9

43



-12.0

-13.0

(a)

(b)

-12.5 -13.5 -13.0

ln(k)

ln(k)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 44 of 46

-13.5

-14.0

-14.0 -14.5 -14.5

-15.0 2.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85 -3

1/T x 10 K

-15.0 2.30

-1

2.35

2.40

2.45

2.50 -3

1/T x 10 K

2.55

2.60

-1

Figure 10

44


Page 45 of 46

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Scheme 1

45



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Table of Content Graphic

46


Page 46 of 46

Activation and Utilization of CO2 Using Ionic Liquid ... - ACS Publications

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