Titanium Phosphate with Flower-like Morphology As an Effective

Article Cite This: Ind. Eng. Chem. Res. 2019, 58, 11779−11786

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Titanium Phosphate with Flower-like Morphology As an Effective Reusable Catalyst for Chemical Fixation of CO2 at Mild Reaction Conditions Arpita Hazra Chowdhury, Ipsita Hazra Chowdhury, and Sk. Manirul Islam* Department of Chemistry, University of Kalyani, Kalyani, Nadia, 741235 West Bengal, India

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S Supporting Information *

ABSTRACT: CO2 insertion reactions draw the attention of researchers today as they could have a major positive impact on the global carbon balance. Flower-like mesoporous titanium phosphate (Ti(HPO4)2·H2O) has been produced by an easy template-free method via refluxing at 50 °C for 18 h. The product is characterized by PXRD, UV−vis, FTIR, N2 adsorption−desorption, FESEM, and TEM studies. The material showed the generation of identical mesopores at 3.9 nm. The titanium phosphate material showed brilliant catalytic activity for the synthesis of cyclic organic carbonates and carbamates with high yields up to 97% and 93%, respectively, via chemical fixation of the greenhouse gas CO2 over different epoxide and amine substrates, respectively, in a solvent-free state at room temperature within a short reaction period. The reusability of the phosphate material has also been examined for 5 cycles for each of the two reactions.

1. INTRODUCTION Conversion of carbon dioxide (CO2) to valuable fine chemicals has attracted the attention1 of researchers from all over the world due to the industrial and environmental viewpoints of CO2 being the most significant greenhouse gas2,3 as well as due to its abundant, nontoxic, nonflammable, and renewable properties. The CO2 insertion reactions may not have a major positive influence on the universal carbon balance, but it is a promising chemical engineering field to recover waste through an environmentally friendly atom-economical process with the formation of fine chemicals. Metal phosphates with layered, open-framework, and porous structures have been effectively synthesized and widely used as important catalyst materials.4 Metal phosphates such as aluminum phosphates, titanium phosphates, and zirconium phosphates have achieved huge attention for their versatile applications as adsorbents,5 electrocatalysts,6 electrodes,7 photocatalysts,8 etc. However, the modified synthesis of metal phosphates and their applications as catalysts to industrially significant organic reactions is still to be explored. As metal phosphates’ surfaces have basic and acidic sites, many catalytic applications as well as CO2 fixation reactions9 could be performed using the acid−base catalysis principle to synthesize industrially important organic compounds by employing the metal phosphates as potentially active heterogeneous catalysts. One of the key significant points of energy and environmental catalysis is to utilize greenhouse gas CO2 for the production of industrially significant chemicals. With this motivation, the fabrication of cyclic carbonates using epoxides and CO2, which are extremely useful ingredients in industrial chemicals and in pharmaceuticals in biomedical production,10−13 is a potential methodology due © 2019 American Chemical Society

the high atom effectiveness of the process resulting from their unique characteristics like high solubility, being less poisonous, and biodegradability. Organic carbamates (RNHCO2R′) are very useful in pharmaceutical and agrochemical (pesticides, herbicides) preparations, and they are utilized in the creation of very significant intermediate product commodity chemicals. 14,15 Generally, both the cyclic carbonates16 and carbamates17 are synthesized using environmentally hazardous phosgene. Therefore, the cycloaddition process of CO2 to epoxide to produce cyclic carbonate18 and CO2 fixation on amines in the presence of alkyl/aryl halides to produce carbamates could be a potential savior.19−22 There are many reports in the literature on the catalytic activity of both homogeneous and heterogeneous systems for CO2 incorporation into cyclic carbonates.23 There are some reported catalysts which can catalyze the carbamate synthesis reaction using CO2. But, those catalytic systems involve strong donor organic solvents and bases.24−29 In the present study, we have reported the mesoporous titanium phosphate (Ti(HPO4)2·H2O) nanomaterial which is synthesized by a cost-effective template-free method. This material is employed as a cheap, reusable heterogeneous catalyst in the case of production of cyclic organic carbonates and carbamates from a range of epoxide and amine substrates by the use of CO2 in solvent-free and mild reaction environments with excellent product selectivity. According to our knowledge, mesoporous Ti(HPO4)2·H2O is a new Received: Revised: Accepted: Published: 11779

March 1, 2019 June 7, 2019 June 13, 2019 June 13, 2019 DOI: 10.1021/acs.iecr.9b01158 Ind. Eng. Chem. Res. 2019, 58, 11779−11786

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Industrial & Engineering Chemistry Research heterogeneous catalyst to be featured in the two CO2 fixation reactions mentioned above.

2. RESULTS AND DISCUSSION 2.1. Characterization of Ti(HPO4)2·H2O Material. 2.1.1. Powder X-Ray Diffraction (PXRD) Analysis. The XRD

Figure 3. FE-SEM images of a Ti(HPO4)2·H2O sample at three different magnifications (a−c).

Figure 1. Powder XRD patterns of a Ti(HPO4)2·H2O sample.

Figure 4. TEM images of a Ti(HPO4)2·H2O sample (a, b) at two different magnifications.

Figure 5. Formation mechanism of the flower-like Ti(HPO4)2·H2O sample.

Scheme 1. Route for Synthesis of (a) Organic Cyclic Carbonates and (b) Epichlorohydrin Carbonate via the CO2 Fixation Reaction

Figure 2. N2 adsorption−desorption isotherm (a) and pore size distribution plot (b) of the Ti(HPO4)2·H2O sample at 77 K.

pattern (Figure 1) of the as-prepared sample signified the presence of α-form of titanium phosphate (α-Ti(HPO4)2· H2O) (JCPDS card no. 44-382) without the presence of any 11780

DOI: 10.1021/acs.iecr.9b01158 Ind. Eng. Chem. Res. 2019, 58, 11779−11786

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Industrial & Engineering Chemistry Research Table 1. Cyclic Carbonate Synthesis Catalysed by Ti(HPO4)2·H2O Nanoparticlea

a Reactions performed under CO2 (1 atm) at room temperature using 30 mg of catalyst, 5 mmol of epoxides, and 1 mmol of co-catalyst without any solvent.

Figure 6. Effect of the (a) amount of TBAB and (b) reaction time on the yield of epichlorohydrin carbonate over mesoporous Ti(HPO4)2· H2O catalyst.

the electronic excitation from the O2− 2p to the Ti4+ 3d orbital of the titanium phosphate sample.30 2.1.4. Surface Area Measurement. The N2 adsorption− desorption isotherm of the Ti(HPO4)2·H2O sample is depicted in Figure 2a which signifies the existence of a type IV isotherm with a H2 hysteresis loop. This type of hysteresis loop confirms the formation of pores with the shape of an ink bottle, having a smaller pore mouth with a bigger pore body.31 The subsequent pore size distribution (PSD) (Figure 2b) resulting from the desorption data of the isotherm showed that the sample has a narrow and uniform pore size distribution with a pore diameter of 3.9 nm which confirmed the development of identical mesopores. The estimated BET surface area and total pore volume of the product were observed to be 30.85 m2 g−1 and 0.048 cm3 g−1, respectively. 2.1.5. Microscopic Analysis. The FESEM images (Figure 3) of the sample showed the flower-like morphology of the sample. It is noticed that the flower-like structure of the sample resulted from the assembly of sheet-like arrangements. This structural feature is confirmed by the TEM image (Figure 4a) of the sample. The high-magnification TEM image of the sample (Figure 4b) confirmed the porous nature of the sample. The EDS result (Figure S3) indicates the existence of Ti, O, and P in the sample. According to the probable formation mechanism, shown in Figure 5, nuclei are initially generated and agglomerated to form nanosheets. With time, the nanosheets are continuously adhered and assembled together to form a flower-like structure. 2.2. Catalytic Activity. 2.2.1. Synthesis of Cyclic Carbonates Catalyzed by Ti(HPO4)2·H2O. The procedure for the preparation of cyclic carbonates using Ti(HPO4)2·H2O material as a catalyst via the CO2 fixation reaction over epoxides in the presence of Bu4NBr (TBAB) is shown in

Figure 7. Conversion and selectivity dependence on reaction time over mesoporous Ti(HPO4)2·H2O catalyst.

impurities. The peak at the 2θ value of 11.5° due to the presence of the (002) plane having an interlayer spacing of 0.76 nm confirmed the layered structure of the sample.5 The crystallite size of the Ti(HPO4)2·H2O material (5.96 nm) was evaluated from the full width at half-maximum (fwhm) and the intensity of the peak of the (002) plane using the Scherrer equation. 2.1.2. FTIR Analysis. The FTIR spectra of the Ti(HPO4)2· H2O nanostructures are depicted in Figure S1. The broad band at about 3443 cm−1 and the sharp peak at 1635 cm−1 correspond to the stretching and bending modes, respectively, of surface-adsorbed water and hydroxyl groups. The FTIR data indicated the phosphorus incorporation into the skeleton in the form of Ti−O−P bonds. The intense peak at 1018 cm−1 indicated the existence of a P−O stretching vibration. The peak at 618 cm−1 is because of the Ti−O vibration mode in the Ti−O−P matrix.30 2.1.3. UV−Vis Analysis. The UV−visible spectra of the material are illustrated in Figure S2. The results showed a broad absorption peak at 245 nm which could be a result from 11781


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Figure 8. Proposed mechanistic route for cyclic carbonate production over Ti(HPO4)2·H2O catalyst.

amount of TBAB was obtained as 1 mmol, while 5 mmol of epichlorohydrin was used as the substrate material. Use of more or less than 1 mmol of TBAB showed partial conversion of epichlorohydrin to epichlorohydrin carbonate. There is also a very important observation that in absence of any catalyst and TBAB only a trace amount of carbonate product was produced. According to Figure 6b, the reaction progressed very fast with reaction time and completed within only 6 h. Therefore, the optimized reaction condition was achieved with 98.5% yield of epichlorohydin carbonate product from 5 mmol of epichlorohydrin in the presence of 1 mmol of TBAB and CO2 (1 atm) using 30 mg of mesoporous Ti(HPO4)2·H2O catalyst in a solvent-free condition. Figure 7 showed that the conversion to the carbonate product from epichlorohydrin increases with growing reaction time and stopped at 98.5% conversion within the first 6 h of reaction, while the epicholorohydrin carbonate product selectivity remained around 100% all through the whole reaction period. When the reaction was performed with only 1 mmol of TBAB in the absence of titanium phosphate catalyst, there was only 32% yield of the epichlorohydrin carbonate product obtained under optimized reaction conditions. Therefore, the porous titanium phosphate catalyst plays an important role in improving the yield of the cyclic carbonate product. The organic cyclic carbonate synthesis through the CO2 fixation reaction using Ti(HPO4)2·H2O catalyst was performed under optimized conditions over several different types of epoxide substrates like epichlorohydrin, allyl glycidyl ether, 1,2epoxy-3-phenoxy propane, styrene oxide, glycidyl isopropyl ether, glycidol, and propylene oxide. Table 1 showed that almost all the epoxides showed excellent yields of the respective carbonate products. It is important to note that generally the aliphatic terminal epoxides (Table 1, entries 1, 2, and 5−7) showed respectively better yields of the cyclic

Scheme 2. Synthetic Route of the Production of (a) Carbamates and (b) Butyl N-Phenyl Carbamate via the CO2 Fixation Reaction

Figure 9. Dependence of the yield and selectivity of butyl N-phenyl carbamate on reaction time over mesoporous Ti(HPO4)2·H2O catalyst.

Scheme 1a. The selected model reaction of the synthesis of epichlorohydrin carbonate from the reaction between epichlorohydrin and CO2 is shown in Scheme 1b. The reaction was optimized by differing parameters such as the amount of TBAB (Figure 6a) and reaction time (Figure 6b) which noticeably affect the product yield as shown in Figure 6a and 6b. According to Figure 6a, the optimized 11782


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Industrial & Engineering Chemistry Research Table 2. Carbamate Synthesis Catalysed by Ti(HPO4)2·H2O Nanoparticlea

a

Reactions performed under CO2 (1 atm) at room temperature for 8 h using 50 mg of catalyst, 2 mmol of amine, and 2 mmol of alkyl/aryl bromide without any solvent.

epoxides using Ti(HPO4)2·H2O as the catalyst is shown in Figure 8. There are large numbers of open active sites present on the 2-dimensional petals’ surface of the flower-like Ti(HPO4)2·H2O surface textured with uniform mesopores. Therefore, CO2 can be easily adsorbed into the pores of the open active sites and readily undergo their fixation reactions. Hence, both the morphology and the textural property of Ti(HPO4)2·H2O are responsible for its remarkably high catalytic activity.33 The Lewis acidic Ti4+ sites of the catalyst activate the epoxide molecules, whereas the Lewis basic O− sites of the catalyst activate the CO2 molecules. The co-catalyst (TBAB) aids the development of the cyclic carbonate product through the ring opening reaction by supplying the leaving group Br−. TBAB forms a halo-alkoxide via interacting with Ti(HPO4)2·H2O catalyst. On the next step, a metal carbonate is formed as the CO2 attacks the metal alkoxide bond, which is on an intramolecular ring-closer reaction step that produces the preferred cyclic carbonate product. 2.2.2. Synthesis of Carbamates Catalyzed by Ti(HPO4)2· H2O. The method for the preparation of carbamates using Ti(HPO4)2·H2O material as the catalyst via the CO2 fixation reaction over amines and alkyl or aryl bromides without utilizing any solvent and base is shown in Scheme 2a. The selected model reaction of synthesis of butyl N-phenyl

Figure 10. Recyclability diagram of mesoporous Ti(HPO4)2·H2O catalyst.

carbonates than the aromatic terminal epoxides (Table 1, entries 3 and 4). The reaction using glycidol as the substrate was performed in the absence of titanium phosphate material under the optimized reaction conditions, and a moderate product yield (50.5%) was obtained because of the influence of hydrogen bonding during the reaction.32 The anticipated reaction mechanism for the development of cyclic carbonates (five-membered) via CO2 fixation over

Table 3. Comparison Chart of Flower-like Ti(HPO4)2·H2O Catalyst with Other Reported Catalysts reaction cyclic carbonate synthesis

carbamate synthesis

catalyst AFS-1 nanomaterial alkylated Zn (salpyr) catalyst mesoporous Ti(HPO4)2· H2O zeolite-beta mesoporous Ti(HPO4)2· H2O

time (h)

reaction condition epichlorohydrin (5 mmol), catalyst (50 mg), RT, Bu4NBr (26.7 mg, 0.083 mmol), 1 atm of CO2 epichlorohydrin (10 mmol), catalyst (0.5 mol %), 80 °C, 1.0 MPa of CO2 epichlorohydrin (5 mmol), catalyst (30 mg), RT, Bu4NBr (1 mmol), 1 atm of CO2 aniline (10 mmol), n-butyl bromide (10 mmol), catalyst (150 mg), CO2 (3.4 bar), 353 K aniline (2 mmol), n-butyl bromide (2 mmol), catalyst (50 mg), RT, 1 atm of CO2 11783

yield (%)

ref

24

92

34

18

38

35

6

97

4

52.8

this study 36

8

93

this study


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Industrial & Engineering Chemistry Research Scheme 3. Synthetic Route of Ti(HPO4)2·H2O Nanomaterial

carbamate from the reaction mixture of aniline, n-butyl bromide, and CO2 is depicted in Scheme 2b. The optimized reaction time was obtained varying the reaction time (Figure 9). Furthermore, there is a very notable observation that in the absence of any catalyst only a trace amount of carbamate product was produced. According to Figure 9, the reaction progressed very rapidly with growing reaction time and completed within only 8 h. Therefore, the optimized reaction condition was achieved with 95% yield of butyl N-phenyl carbamate product from 2 mmol of aniline and 2 mmol of n-butyl bromide in the presence of CO2 (1 atm) using 50 mg of mesoporous Ti(HPO4)2·H2O catalyst in a solvent-free condition. It can be noticed from Figure 9 that the CO2 fixation reaction proceeded with almost 100% N-phenyl carbamate product selectivity throughout the whole reaction period. The carbamate synthesis through the CO2 fixation reaction using Ti(HPO4)2·H2O catalyst was performed under optimized conditions over amines like aniline and m-chloroaniline with bromides like butyl bromide and benzyl bromide. Table 2 showed that aniline with alkyl bromide (Table 2, entry 1) showed a better result than amine with an electron retreating group and aryl bromide (Table 2, entries 2−4). 2.3. Recyclability of Ti(HPO4)2·H2O Catalyst. To understand one of the key features of a heterogeneous catalyst, i.e., catalyst life, we have screened the recyclability of the Ti(HPO4)2·H2O catalyst for both of the CO2 fixation reactions. The reusability experiment was performed by isolating the catalyst from the reaction mixture via centrifugation, after reaction completion. The catalyst was made impurity free by washing it multiple times with DI water and ethyl acetate and was dried at 50 °C in an oven for 2 h. The catalyst was recovered successfully and was utilized in both the CO2 fixation reactions for 5 times with almost no catalyst deactivation, showing the brilliant yield of the products

(Figure 10). Histograms (Figure S4) related to Figure 10 are given in the Supporting Information. There is no evident change in the structure of the catalyst after recycling found in the catalyst, which is supported by the FTIR spectra (Figure S5) and FESEM images (Figure S6) of the reused catalyst. This observation signifies that the flower-like Ti(HPO4)2·H2O catalyst has outstanding recycling efficiency for both of the CO2 fixation reactions. Table 3 shows a comparative chart of the efficiency of our Ti(HPO4)2·H2O catalyst and catalytic system with some formerly reported catalytic systems. It can be observed from Table 3 that the Ti(HPO 4) 2 ·H 2O catalyst showed a comparatively better yield of the desired carbonate product with shorter reaction time than the other reported catalysts. The Ti(HPO4)2·H2O catalyst also showed the better yield of the desired carbamate product at room temperature and under 1 atmospheric pressure of CO2 than the other reported catalyst.

3. CONCLUSIONS Mesoporous Ti(HPO4)2·H2O catalyst is synthesized via an easy template-free technique with flower-like morphology forming from the agglomeration of the Ti(HPO4)2·H2O nanosheets. This material showed brilliant catalytic efficiency for CO2 fixation reactions like cyclic carbonate and carbamate synthesis at 1 atm CO2 pressure with very gentle reaction conditions. The reactions were performed without utilizing any solvent at room temperature. Additionally, excellent selectivity of the needed products and brilliant catalyst recyclability are observed, suggesting that the mesoporous Ti(HPO4)2·H2O material as a potentially active new heterogeneous catalyst for chemical fixation of CO2. 11784


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4. EXPERIMENTAL SECTION 4.1. Materials. Titanium isopropoxide (TIP), phosphoric acid, and 85% (w/w) sodium sulfate (Na2SO4) were obtained from Merck, India. All solvents, epoxides, and amines were obtained from Sigma-Aldrich. DI water was utilized for all throughout experiments. 4.2. Synthesis of Ti(HPO4)2·H2O Nanomaterial. The titanium phosphate nanomaterial was synthesized via a simple template-free technique (Scheme 3) using titanium isopropoxide as the precursor. First, 3 mmol of titanium isopropoxide was dissolved in 30 mL of ethanol, and the mixture was stirred for 1 h at room temperature. Next, 3 mL of 85% (w/w) phosphoric acid was mixed dropwise with the reaction solution, and then the mixture was refluxed at 50 °C for 18 h. After the system refluxed, the system was cooled, and a white product was then collected after it was washed with DI water and dried at 50 °C under vacuum. 4.3. Procedure for Synthesis of Cyclic Carbonate from Epoxides using Mesoporous Ti(HPO4)2·H2O Nanomaterial. The carbonate synthesis was executed at room temperature by mixing 5 mmol of epoxide, 1 mmol of Bu4NBr, and 30 mg of Ti(HPO4)2·H2O catalyst in a round-bottom flask, equipped with a balloon containing CO2 under 1 atm. After 6 h, the solid catalyst was collected through centrifugation. After washing with DI H2O, the organic portion was dried over anhydrous Na2SO4. The isolated cyclic carbonate products were characterized by 1H NMR and 13C NMR spectroscopy. 4.4. Procedure for Synthesis of Carbamates using Mesoporous Ti(HPO4)2·H2O Nanomaterial. The carbamate synthesis was done at room temperature by mixing aniline (2 mmol), n-butyl bromide (2 mmol), and Ti(HPO4)2·H2O catalyst (50 mg) in a round-bottom flask, set with a CO2containing balloon under 1 atm. After 8 h of reaction, ethyl acetate was added to the reaction mixture for dilution. The solid catalyst was collected through centrifugation. After washing with DI H2O, the organic portion was dried over anhydrous Na2SO4. The isolated carbamate product was characterized by 1H NMR and 13C NMR spectroscopy.

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Sciences (BRNS), Government of India (37(2)/14/03/2018BRNS/37003) for providing financial support. A.H.C. is thankful to the University of Kalyani, India, for providing her URS fellowship. I.H.C. is thankful to CSIR, India (09/106 (0181) 2019 EMR-I) for her fellowship. S.M.I. is also thankful to CSIR (02(0284)2016/EMR-II dated 06/12/2016), New Delhi, Government of India, for financial support. The authors sincerely acknowledge the UGC and DST, New Delhi, Government of India, for allotting a grant under the FIST, PURSE, and SAP program to the Department of Chemistry, University of Kalyani.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecr.9b01158. Characterization details; FTIR, UV−vis, and EDAX pattern analyses of the catalyst material; histograms of the recyclability tests; FTIR and FESEM images of recycled catalyst; and 1H NMR and 13C NMR data of the isolated products (PDF)

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REFERENCES

AUTHOR INFORMATION

Corresponding Author

*E-mail: manir65@rediffmail.com. ORCID

Sk. Manirul Islam: 0000-0002-3970-5468 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS S.M.I. is thankful to DST-SERB (EMR/2016/004956), New Delhi, Government of India, Board of Research in Nuclear 11785


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