Journal of Materials Science

Zinc Metalated Porous Organic Polymer Catalyzed Chemical Fixation of CO2 to

Epoxides
--Manuscript Draft--

Manuscript Number:

Full Title: Zinc Metalated Porous Organic Polymer Catalyzed Chemical Fixation of CO2 to
Epoxides

Article Type: Manuscript (Regular Article)

Keywords: *Porous Organic Polymer *CO2 cycloaddition *epoxide *cyclic carbonate

*triethylenetetramine

Corresponding Author: Sanfaori Brahma, PhD

Gauhati University Department of Chemistry
Guwahati, Assam INDIA

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Gauhati University Department of Chemistry

Corresponding Author's Secondary

Institution:

First Author: Sanfaori Brahma, PhD

First Author Secondary Information:

Order of Authors: Sanfaori Brahma, PhD

Naranarayan Deori, Masters in Chemistry

Surabhi Lahkar, Masters in Chemistry

Saurav Paul, Masters in Chemistry

Rakhimoni Borah, Masters in Chemistry

Order of Authors Secondary Information:

Abstract: Abstract: A facile metalation of organic polymer, Te-TETA obtained from

terephthalaldehyde and triethylenetetramine, with zinc to produce metalated porous
organic polymer, Te-TETA-Zn has been reported here. Both Te-TETA and Te-TETA-
Zn were analyzed by various analytical techniques viz. FTIR, PXRD, FE-SEM, EDX
and XPS. A huge transformation from the spherical morphology of Te-TETA to the
flake like structure in TE-TETA-Zn can be seen in the FE-SEM images advocating the
successful coordination of zinc with the N-coordinating sites. An investigation of the
catalytic activity of Te-TETA-Zn in combination with tetrabutylammonium bromide
(TBAB, 2 mol%) reveals it to be an efficient heterogeneous catalyst component for the
chemical fixation of CO2 to epoxides producing cyclic carbonate products ( up to 99%
conversion) under reaction conditions [Te-TETA-Zn (20 mg), TBAB (2 mol%), 5 bar
CO2 pressure, 60 °C, 4 h].

Funding Information: Science and Engineering Research Dr Sanfaori Brahma

Board, India
(SERB/F/8533/2015-16)

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Cover Letter Click here to access/download;Cover Letter;Cover
letter_Sanfaori.pdf

Dr Sanfaori Brahma, PhD (Indian Institute of Technology Kanpur)

Assistant Professor,
Department of Chemistry, Gauhati University
Guwahati-781014 (INDIA)
Phone: +91-9101165193
Email: sanfaoribrahma@gmail.com; sanfaori@gauhati.ac.in; sanfaori123@gmail.com

Date: 24-May-2023
To,
Dear Prof. C. Barry Carter,
Editor-in-Chief, Journal of Materials Science
We are submitting our manuscript entitled “Zinc metalated porous organic polymer
catalyzed chemical fixation of CO2 to epoxides” authored by Naranarayan Deori, Surabhi
Lahkar, Saurav Paul, Rakhimoni Borah and Sanfaori Brahma* for the consideration of the work to
be published as a regular paper in your J. Mater. Sci.

The importance of this work can be justified as follows:

Only a few reports of metalated porous organic polymer have been found that acts as a
heterogeneous catalyst for the cycloaddition of CO2 to epoxides producing cyclic carbonates.

1. Facile metalation of terephthalaldehyde-triethylenetetramine organic polymer (Te-TETA)

with zinc was performed yielding zinc metalated POP, Te-TETA-Zn.
2. Characterization of both Te-TETA and Te-TETA-Zn were done by FTIR, PXRD, FE-SEM,
EDX and XPS.
3. A huge morphological transformation from spherical structure of Te-TETA to flattened
structure of Te-TETA-Zn was evident from FE-SEM images, which may due to the
conformational change of free TE-TETA upon metalation with zinc.
4. Te-TETA-Zn POP in combination with tetrabutylammonium bromide (TBAB) co-catalyst
acts as an excellent heterogeneous catalyst for the chemical fixation of CO2 to epoxides
producing cyclic carbonates (90 - 99 % conversions) under mild reaction conditions [Te-
TETA-Zn (20 mg), TBAB (2 mol%), 5 bar CO2 pressure, 60 °C, 4 h].

Thanking you,

Best regards
Dr. Sanfaori Brahma
(Corresponding author)
Manuscript Click here to
access/download;Manuscript;Manuscript_sanfaori.pdf
Click here to view linked References

Zinc Metalated Porous Organic Polymer Catalyzed Chemical Fixation of

1
2 CO2 to Epoxides
3
4 Naranarayan Deori, a Surabhi Lahkar,a Saurav Paul,a Rakhimoni Boraha and Sanfaori Brahma*a
5
a
6 Department of Chemistry, Gauhati University, Guwahati 781014, Assam, India
7 E-mail: sanfaori123@gmail.com; sanfaori@gauhati.ac.in
8 ORCID: 0000-0002-7884-2692
9
10
11 Abstract: A facile metalation of organic polymer, Te-TETA obtained from
12
13 terephthalaldehyde and triethylenetetramine, with zinc to produce metalated porous organic
14
15 polymer, Te-TETA-Zn has been reported here. Both Te-TETA and Te-TETA-Zn were
16 analyzed by various analytical techniques viz. FTIR, PXRD, FE-SEM, EDX and XPS. A huge
17
18 transformation from the spherical morphology of Te-TETA to the flake like structure in TE-
19
20 TETA-Zn can be seen in the FE-SEM images advocating the successful coordination of zinc
21
22 with the N-coordinating sites. An investigation of the catalytic activity of Te-TETA-Zn in
23
24 combination with tetrabutylammonium bromide (TBAB, 2 mol%) reveals it to be an efficient
25
26 heterogeneous catalyst component for the chemical fixation of CO2 to epoxides producing
27 cyclic carbonate products ( up to 99% conversion) under reaction conditions [Te-TETA-Zn
28
29 (20 mg), TBAB (2 mol%), 5 bar CO2 pressure, 60 °C, 4 h].
30
31
32
33 1. INTRODUCTION
34
35 As humanity advances, daily consumption of fossil fuel as a source of energy is increasing,
36
37 producing more and more CO2, a critical component of greenhouse gases that contribute to
38
39 climate change. To mitigate this problem, carbon dioxide capture and storage/utilization
40
41 (CCS/U) had emerged as a sustainable approach for reducing CO2 concentration.1-6 Among
42
43 numerous CO2 functionalization techniques, conversion of CO2 to various non-toxic useful
44
45
chemicals such as cyclic carbonates via CO2/epoxide coupling had gained much interest among
46 the scientists due to the atom efficiency and high selectivity nature of the reaction. 7-12 Cyclic
47
48 carbonates are industrially very useful chemical which serve as electrolyte in Li-ion batteries,14
49
50 precursor for pharmaceuticals,13 dyes,13 polymers,15, 16 and other fine chemicals.17 Moreover,
51
52 cyclic carbonates are excellent non-protic solvents.18 Hence designing both homogeneous and
53
54 heterogeneous catalytic systems such as metal complexes,19-21 ionic liquids,22-25
55
56
organocatalysts,26-28 H-bond donor compounds,29-31 metal organic frameworks (MOFs),32-37
57 porous organic frameworks (POFs)38-47 etc. have gained attention for synthesizing cyclic
58
59 carbonates through cycloaddition reaction of CO2 to epoxides.
60
61
62
63
64
65
 Porous organic polymers (POPs) are formed through strong covalent bonds among the
1
2 monomers with large surface area, tunable pore size, high stability and controllable chemical
3
4 composition.48, 49 POPs could be divided to amorphous POPs that include hyper-crosslinked
5
polymers (HCPs), conjugated microporous polymers (CMPs), polymers of intrinsic
6
7 microporosity (PIMs) and porous aromatic frameworks (PAFs) whereas crystalline POPs that
8
9 includes covalent organic frameworks.50 Over the last decade, POPs have emerged as an
10
11 efficient heterogeneous catalyst and showed promising applications in different fields of
12
13 research such as adsorption and separation, energy storage, catalysis, etc.51, 70 The specific
14
15 designable synthetic strategies via selecting functional monomers make POPs promising
16 catalyst for transformation of CO2 to other valuable materials.51 Various POP derived non-
17
18 metalated and metalated catalytic systems have been developed for efficient CO2 capture and
19
20 transformation. Zhao and co-workers52 reported perfluorinated covalent triazine framework
21
22 (FCTF-1) for superior CO2 adsorption and CO2/N2 separation under equilibrium and kinetic
23
24 conditions compared to their non-fluorinated counterparts. Zhang and co-workers53 reported
25
26 tertiary phosphorus and quaternary phosphonium functionalized microporous ionic polymers
27 synthesized via homopolymerization with different counter ions in which the cationic part acts
28
29 as a catalyst for the cycloaddition reaction of CO2 to epoxides. Yang and co-workers54 reported
30
31 a series of fluorine functionalized polymer ionic liquids (F-PILs) having imidazolium cations
32
33 and chloride or bromide anions that act as an efficient catalyst for CO2 cycloaddition reaction
34
35 with epoxides producing cyclic carbonates. However, only a few reports of metalated POP
36
37
catalyst for the CO2 cycloaddition reaction were found. Wang’s group55 reported Zn and Co
38 metalated porphyrin based 2D COFs, COF-366-M and COF-SQ-M that act as an excellent
39
40 heterogeneous catalysts for the cycloaddition reaction of epoxides and CO2. Mohamed and co-
41
42 workers56 reported a Cr and Co metalated novel salen-based POP catalyst for the cycloaddition
43
44 of CO2 with epoxides showing excellent catalytic activity. Xiao and co-workers57 reported
45
46 bipyridine based metalated porous organic polymer (M/POP-Bpy, M= Cu, Co, Zn) that exhibit
47
48
efficient catalytic activity in the cycloaddition reaction of CO2 with epoxides. Yang and co-
49 workers58 reported metalated salen based COF (COF-salen-M, M= Co, Mn, Cu, Zn) catalyst
50
51 for fixing CO2 with epoxides. Zhang et al.59 reported novel N-rich azo-linked porous
52
53 frameworks that act as efficient CO2 adsorbents with high CO2/N2 selectivity which on further
54
55 metalation with Zn, acts as a catalyst for CO2 cycloaddition reaction to epoxides. Gao and co-
56
57 workers60 reported Co metalated ionic porhyrin based COF (Co(II)@TA-TF COF) that exhibit
58
very high CO2 adsorption capabilities and also acts as an excellent catalyst in the catalytic
59
60 cycloaddition of CO2 to epoxides. Meng and co-workers61 reported porous Zn metalated Poly-
61
62
63
64
65
 melamine-formaldehyde POF that acts as a highly efficient catalyst for chemical fixation of
1
2 CO2 to epoxides producing cyclic carbonates. Wu’s group62 reported Co doped
3
4 metalloporphyrin based POPs (Co-PPOPs) that exhibit high catalytic activity towards the
5
cycloaddition reaction of CO2 to epoxides. Recently, our group reported Cr(III) metalated
6
7 melamine-terephthalaldehyde porous organic framework nanosheet [MT-Cr(III) POFN]63
8
9 catalyst for the chemical fixation of CO2 to epoxides that exhibits substrate selective catalytic
10
11 activity. Herein, in this report, we have reported Zn metalated terephthalaldehyde-
12
13 triethylenetetramine POP (Te-TETA-Zn) as heterogeneous catalyst for chemical fixation of
14
15 CO2 to epoxides that yield cyclic carbonates in presence of tetrabutylammonium bromide
16 (TBAB) co-catalyst.
17
18
19 2. RESULTS AND DISCUSSION
20
21 2.1 Synthesis of terephthalaldehyde-triethylenetetramine (Te-TETA) organic
22
23 polymer. The synthesis of Te-TETA organic polymer was accomplished following the
24
25 reported procedure of Sun et al.64 with a little modification as shown in Scheme 1. Typically
26
to a 2 mmol solution of triethylenetetramine (TETA) in acetonitrile kept in ice bath, 2 mmol
27
28 terephthalaldehyde solution in acetonitrile was added dropwise with vigorous stirring. After
29
30 the addition of terephthalaldehyde solution, the mixture was stirred for another 2 hours. Then
31
32 the solvent was evaporated and yellow gel-like product obtained was converted to powder by
33
34 adding dichloromethane. The powder was collected and washed with acetonitrile and
35
36 dichloromethane, respectively, and dried at room temperature to get the porous organic
37 polymer, Te-TETA.
38
39
40
41
42
43
44
45
46
47
48
49
50 2.2 Synthesis of Zn metalated Te-TETA POP (Te-TETA-Zn). The as-synthesized Te-
51
52 TETA was added to DMF solvent and stirred for 30 minutes. To this excess amount of ZnBr2
53
54 in DMF was added and stirred at room temperature for 24 hours. The resulting solution was
55
56 evaporated to dryness and then methanol was added. Yellow precipitate obtained was washed
57
with water and methanol subsequently and dried in air to obtain metalated Te-TETA-Zn,
58
59 which were further characterized by FTIR, PXRD, XPS and FESEM-EDX.
60
61
62
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
3. CHARACTERIZATION
12 3.1 Powder X-ray Diffraction Analysis. The wide angle PXRD of the as-synthesized Te-
13
14 TETA shows broad peaks around 2θ = 22° and 42° (Figure 1, black trace) signifying the
15
16 formation of amorphous polymer network.65 Moreover, absence of crystalline peaks signifies
17
18 complete formation of the polymeric network. PXRD of as-synthesized Te-TETA-Zn (Figure
19
20 1, red trace) shows a broad peak at 2θ = 26° and 45° suggesting the retention of the amorphous
21
polymer network. Appearance of new sharp peaks at 2θ = 14°, 19°and 26° might be due to the
22
23 establishment of some short-range orders as a result of ZnBr2 intake in the polymer.67
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38 Figure 1. Powder X-ray diffraction pattern of Te-TETA (black trace) and Te-TETA-Zn (red
39
40 trace).
41 3.2 FT-IR analysis. The FT-IR spectrum of Te-TETA (Figure 2, black trace) shows a sharp
42
43 peak at 1641 cm-1 establishing the existence of imine linkage (-HC=N-) in the synthesized
44
45 organic polymer. Moreover, presence of peaks at 2935 and 2858 cm-1 corresponding to
46
47 methylene groups (-CH2-) of TETA signifies the incorporation of the TETA moiety in the
48
49 polymeric structure.68 Absence of characteristic peaks at 1687 cm-1 corresponding to C=O of
50
51 terephthalaldehyde and at 3279 and 3361 cm-1 corresponding to -NH2 of TETA in the Te-
52 TETA indicates the complete formation of imine link in the polymer (Figure S1, ESI). The
53
54 FTIR spectrum of Te-TETA-Zn (Figure 2, red trace) resembles the parent Te-TETA
55
56 implicating retention of polymeric structure in Te-TETA-Zn. Moreover, appearance of broad
57
58 peaks at around 3400-3500 cm-1 is attributable to the absorbed moisture in both Te-TETA and
59
60 Te-TETA-Zn.69
61
62
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 Figure 2. FTIR spectra of Te-TETA (black trace) and Te-TETA-Zn (red trace).
17
18
19
20 3.3 FE-SEM analysis. Surface morphology of the synthesized Te-TETA and metalated Te-
21 TETA-Zn were investigated by FE-SEM. The FE-SEM images of Te-TETA (Figure 3A and
22
23 3B) reveal nicely shaped spherical structure of the polymer in the range of 1-3 µm. However,
24
25 upon metalation of Te-TETA with zinc, a porous structure with flattened surface morphology
26
27 was obtained as revealed by FE-SEM images (Figure 3C and 3D). Elemental composition of
28
29 Te-TETA determined from SEM-EDX analysis estimates atomic percentage to be C (61%), N
30
31 (31%) and O (7%) (Figure S2, ESI) and that of Te-TETA-Zn to be C (54%), N (18%), O (5%),
32 Zn (9%) and Br (13%) (Figure S3, ESI). Oxygen appeared due to absorbed moisture. Thus, the
33
34 EDX report of Te-TETA-Zn provides clear evidence of the successful metalation of Te-TETA
35
36 with Zn.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59 Figure 3. FE-SEM images of Te-TETA (A and B) and Te-TETA-Zn (C and D).
60
61
62
63
64
65
 3.4 Thermogravimetric analysis (TGA). Thermal stability of Te-TETA and Te-TETA-Zn
1
2 were monitored by TGA under N2 atmosphere with heating rate of 20 °C min−1 (Figure 4). The
3
4 TGA curve of Te-TETA shows that Te-TETA is stable up to 250 °C where it starts to
5
decompose due to the degradation of imine linkage.71 However, TGA curve of Te-TETA-Zn
6
7 reveals that the stability of the metalated Te-TETA increases up to 410 °C due to the
8
9 incorporation of zinc making Te-TETA more robust.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Figure 4. TGA curve of Te-TETA POP (black trace) and Te-TETA-Zn (red trace).
27
28 3.5 XPS Analysis. XPS survey report of Te-TETA (Figure 5A) shows peaks at 285 eV for
29
30 C1s, 399 eV for N1s and 533 eV for O1s. Appearance of peak due to oxygen might be
31
32 attributable to absorbed moisture. XPS survey report of Te-TETA-Zn (Figure 5B) shows peaks
33
34 at 68 eV for Br3d, 182 and 188 eV for Br3p, 256 eV for Br3s, 285 eV for C1s, 400 eV for N1s,
35
36 533 eV for O1s and 1022 and 1045 eV for Zn2p. XPS survey report clearly indicates the intake
37 of ZnBr2 moiety in the POP.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Figure 5. XPS survey report of Te-TETA (A) and Te-TETA-Zn (B).
58
59
60
61
62
63
64
65
 4. CATALYTIC STUDIES
1
2 The catalytic activity of the as-synthesized Te-TETA-Zn along with TBAB co-catalyst was
3
4 investigated in the cycloaddition reaction of CO2 to epoxides producing cyclic carbonates
5
(Table 1) as shown in Scheme 3.
6
7
8
9
10
11
12
13
14
15
16
17
18
19 To study the catalytic activity in the cycloaddition reaction of CO2 to epoxides, the substrate
20
21 along with co-catalyst TBAB were loaded in a stainless steel autoclave equipped with a
22
23 magnetic stir bar and heater. Pre-existing air was purged off by purging CO2 and then
24
25 appropriate pressure of CO2 and temperature was applied. The reaction was carried out for
26
27 desired time and after the completion of the reaction the products were collected and
28 centrifuged to remove the catalyst. Formation of cyclic carbonate product was confirmed by
29
30 1
H NMR showing downfield shifting of the characteristic peaks as compared to epoxides. The
31
32 FTIR spectrum also shows strong characteristic peaks around 1780-1790 cm-1 corresponding
33
34 to ν (C=O) of the cyclic carbonate moiety. Percentage conversion (% conv.) of the product was
35
36 determined using the formula illustrated in Figure S4 (ESI). 1H NMR and FTIR spectra of the
37
38 crude reaction mixtures are illustrated in Figures S5-S17.
39 Table 1. Cycloaddition of CO2 to epoxides catalyzed by Te-TETA-Zn catalyst.
40
41
42 Entry Epoxides Catalyst [mg] Co-Catalyst % conv. Ref.
43 (mmol)
44
45 1 ECH Te-TETA-Zn [20] 2 >99 Tw
46 2 ECH Te-TETA [20] 2 56 Tw
47
48 3 ECH Te-TETA-Zn [20] 0 Trace Tw
49 4 ECH 0 2 32 62
50 5 EBH Te-TETA-Zn [20] 2 >99 Tw
51
52 6 AGE Te-TETA-Zn [20] 2 >99 Tw
53 7 BGE Te-TETA-Zn [20] 2 >99 Tw
54
55 8 SO Te-TETA-Zn [20] 2 90 Tw
56 Reaction parameters: p(CO2) = 5 bar; Time = 4 h; Temperature = 60°; ECH: 500
57
µL (6.4 mmol), EBH: 500 µL (5.9 mmol), SO: 500 µL (4.4 mmol), AGE: 500 µL
58
59 (mmol), BGE: 500 µL (3.5 mmol).
60
61
62
63
64
65
 Initially, the cycloaddition of CO2 with epichlorohydrin (ECH) has been performed by
1
2 taking ECH, Te-TETA-Zn catalyst and co-catalyst TBAB in a reaction vessel and pre-existing
3
4 air was removed by purging CO2. The reaction was carried out for 4 h at 5 bar CO2 pressure
5
and 60 °C temperature, which shows >99 % conversion (entry 1) to the corresponding cyclic
6
7 carbonate. To examine the importance of Zn, the same reaction was carried out using Te-
8
9 TETA as catalyst along with TBAB, which showed 56% conversion (cf. entries 1 and 2).
10
11 However, in the absence of co-catalyst TBAB, only a trace amount of cyclic carbonate was
12
13 obtained when Te-TETA-Zn was used alone (entry 3). However, TBAB alone could result
14
15 32% conv. Of ECH to its corresponding cyclic carbonate (entry 4). The higher conversion
16 shown by Te-TETA/TBAB compared to TBAB alone might be due to the presence of -NH-
17
18 groups that activate the epoxide through H-bond donor interactions with the epoxide O-atom
19
20 (cf. entries 2 and 4).63 With other epoxides such as epibromohydrin (EBH), allyl glycidyl ether
21
22 (AGE) and butyl glycidyl ether (BGE), >99% conversions (entries 5, 6 and 7) were achieved
23
24 under the same reaction conditions [60 °C, 5 bar p(CO2), 4 h]. However, styrene oxide (SO)
25
26 showed relatively lower 90 % conversion (entry 8).
27
28
29 4.1 Catalytic cycle. Based on previously reported DFT studies29, 72 and experimental findings
30
31 a plausible mechanism for the catalytic cycloaddition reaction of CO2 to epoxides producing
32
33 corresponding cyclic carbonates can be illustrated as shown in Scheme 4. Initially, the epoxide
34
35 substrate gets activated via coordination with the Lewis acidic Zn metal center. Thereafter the
36
37
Br- ion of TBAB co-catalyst attacks a less hindered C-atom of epoxide to open the epoxide
38 ring followed by CO2 insertion and ring cyclization, producing corresponding cyclic carbonate.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56 Scheme 4. Plausible catalytic cycle for producing cyclic carbonates from cycloaddition of CO2
57
58 to epoxide.
59
60
61
62
63
64
65
 5. CONCLUSIONS
1
2 In summary, Te-TETA organic polymer was synthesized and characterized by PXRD, FTIR,
3
4 FE-SEM and XPS analysis. FT-IR spectroscopy strongly supports the formation of imine
5
linkage (-HC=N-) that results from the condensation of aldehyde and amine functional groups
6
7 of terephthalaldehyde and triethylenetetramine (TETA) by showing strong resonance at 1641
8
9 cm-1. Broad peaks at around 2θ = 22° and 42° in the PXRD of Te-TETA with no additional
10
11 crystalline peaks signifies complete formation of an amorphous polymer network. Its
12
13 successful metalation with zinc was confirmed from SEM-EDX analysis, and XPS analysis
14
15 showing characteristic peaks for Zn at 1022 and 1045 eV corresponding to Zn2p in XPS
16 spectrum. Further, retention of Br atoms in Te-TETA-Zn is evidenced from the peaks in the
17
18 XPS survey report at 68 eV (Br3d), 182 and 188 eV (Br3p), and 256 eV (Br3s). Moreover, a
19
20 distinguishable difference observed in the PXRD spectra of Te-TETA and Te-TETA-Zn with
21
22 the appearance of more peaks in the spectrum of Te-TETA-Zn might be a consequence of Zn
23
24 coordination to TE-TETA. FE-SEM images illustrates aggregated uniform sphere in TE-
25
26 TETA and flattened porous structure in Te-TETA-Zn. This huge morphological change from
27 spherical structure in Te-TETA to flattened porous structure in Te-TETA-Zn can be attributed
28
29 to the coordination of Zn to the available N-binding sites. The as-synthesized porous Te-
30
31 TETA-Zn acts as an efficient heterogeneous catalyst in presence of co-catalyst TBAB for the
32
33 CO2/epoxide coupling reaction to yield cyclic carbonate product showing 90 - 99% conversions
34
35 under the reaction conditions [5 bar CO2 pressure, 60 °C, 4 h]. However, in absence of the Te-
36
37
TETA-Zn catalyst, TBAB alone could result in only 32% conversion under the same reaction
38 condition when epichlorohydrin was taken as substrate.
39
40
41
42 6. EXPERIMENTAL SECTION
43
44 6.1 Materials. All commercially available starting materials and solvents were purchased
45
46 and used as received.
47 1
48
6.2 Instrumentation. H NMR spectra were recorded on a Bruker 300 MHz
49 spectrophotometer with Tetramethylsilane (TMS) as the internal standard using CDCl3 solvent.
50
51 FE-SEM images were taken in the ZEISS Sigma 300 FE-SEM instrument. IR spectra were
52
53 recorded in Bruker ALPHA II ECO-ATR. Powder XRD spectra were recorded in Rigaku
54
55 Ultima IV X-ray powder diffractometer operating a Cu Kα-X-ray source, equipped with a Ni
56
57 filter to suppress Kβ emission and a D/teX ultra high speed position sensitive detector. XPS
58
data were recorded in an X-ray Photoelectron Spectrometer (ESCALAB Xi+, Thermo Fisher
59
60 Scientific Pvt. Ltd., UK) with monochromatic AlKα radiation. Thermogravimetric analysis
61
62
63
64
65
 (TGA) was performed on a Mettler Toledo instrument with a temperature range of 25−700 °C
1
2 and a heating rate of 20 °C min−1.
3
4 6.3 Synthesis of terephthalaldehyde-triethylenetetramine (Te-TETA) organic
5
polymer. To a 2 mmol (292 mg) solution of triethylenetetramine in acetonitrile (10 mL) kept
6
7 in ice bath, a solution of 2 mmol (268 mg) terephthalaldehyde in acetonitrile (10 mL) was
8
9 added dropwise with vigorous stirring. After the addition was complete, the mixture was stirred
10
11 for 2 hours. Then the solvents were evaporated using rotary evaporator. Yellow gel-like product
12
13 was obtained which was readily transformed into solid by adding dichloromethane solvent (15
14
15 mL). The solid product was thencollected, washed with acetonitrile and dichloromethane,
16 respectively and subsequently dried at room temperature to get the yellow powder, Te-TETA.
17
18 6.4 Synthesis of Te-TETA-Zn. 200 mg of the synthesized Te-TETA was added in 10 mL
19
20 DMF and stirred for 30 minutes. To this solution, 200 mg of ZnBr2 in 10 mL DMF was added
21
22 and stirred for 24 h at room temperature. The resulting solution was evaporated to dryness and
23
24 10 mL methanol was added. Yellow precipitate formed which was further washed with water
25
26 and methanol, respectively and then dried at room temperature.
27 6.5 General procedure for chemical fixation of CO2 to epoxides. The catalytic CO2
28
29 fixation reactions with epoxides to form cyclic carbonates were carried out in a stainless steel
30
31 autoclave equipped with a magnetic stir and an inbuilt heater. A mixture of substrate (epoxide),
32
33 catalyst and co-catalyst in a specific ratio was taken in the stainless steel autoclave and purged
34
35 with CO2 gas for around 1 minute and then an appropriate CO2 pressure was applied. The
36
37
reaction was carried out for a desired time period at a particular temperature. After the
38 completion of the reaction, the crude reaction mixture was taken out from the reaction vessel
39
40 and centrifuged at 14000 rpm for 5 minutes to separate the catalyst. 1H NMR and FTIR spectra
41
42 were then recorded for the confirmation of cyclic carbonate product formation. % Conversions
43
44 of epoxides to cyclic carbonate products were calculated by using the formula shown in Figure
45
46 S4.
47
48
49 Conflicts of interest
50
51 There are no conflicts of interest to declare.
52
53
54
55 Acknowledgements
56
57 The authors thank DST-SERB, India for financial support. The authors would like to thank the
58
Indian Institute of Technology Guwahati (IITG), North East Institute of Science and
59
60 Technology (NEIST), Jorhat for providing various instrumental facilities.
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 Keywords: •Porous Organic Polymer •CO2 cycloaddition •epoxide •cyclic carbonate
1
2 •triethylenetetramine
3
4
5
6
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