Honeycomb-structured solid acid catalysts fabricated via the swelling-induced self-assembly of acidic poly(ionic liquid)s for highly efficient hydrolysis reactions

doi:10.1016/S1872-2067(20)63658-0

Abstract

Abstract:

The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging. In this study, acidic poly(ionic liquid)s with swelling ability (SAPILs) were designed and synthesized via the free radical copolymerization of ionic liquid monomers, sodium p-styrenesulfonate, and crosslinkers, followed by acidification. The ³¹P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength. The thermogravimetric analysis results in the temperature range of 300-345 °C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H) (245 °C). Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional (3D) honeycomb structure in water, which was ascribed to the swelling-induced self-assembly of the molecules. Moreover, we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol, and determined that their catalytic activity was much higher than that of homogeneous acid catalysts. The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures. Depending on the reaction mixture, the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5-23.3 times higher than that outside of it, which suggested the high enrichment ability of SAPILs for cyclohexyl acetate. The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate, which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.

Key words: Heterogeneous acid catalyst, Acidic poly(ionic liquid), Swelling, 3D honeycomb structure, Enrichment, Hydrolysis, Hydration

Bihua Chen, Tong Ding, Xi Deng, Xin Wang, Dawei Zhang, Sanguan Ma, Yongya Zhang, Bing Ni, Guohua Gao. Honeycomb-structured solid acid catalysts fabricated via the swelling-induced self-assembly of acidic poly(ionic liquid)s for highly efficient hydrolysis reactions[J]. Chinese Journal of Catalysis, 2021, 42(2): 297-309.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63658-0

https://www.cjcatal.com/EN/Y2021/V42/I2/297

Figures/Tables 13

Scheme 1. Schematic illustration of the synthesis process of acidic poly(ionic liquid)s with swelling ability (SAPILs). Here AIBN, VSIm, VSbIm, [EG3(Vim)2]Br2, and [O(Vim)2]Br2 denote 2,2?-azobisisobutyronitrile, 1-vinyl-3-(3-sulfopropyl)imidazolium, 1-vinyl-3-(4-sulfobutyl)imidazolium, 1,8-triethylene glycoldiyl-3,3?-divinylimidazolium bromide, and 1,8-dioctyl-3,3?-divinylimidazolium bromide, respectively.

Table 1 Conditions for the synthesis of acidic poly(ionic liquid)s with swelling ability (SAPILs) and their swelling ratios (Q) in water.c

Sample	IL^a (mmol)	NaSS^b (mmol)	Crosslinker (mmol)	Q (g/g)
SAPIL-1	4.875	4.875	0.25	24.5
SAPIL-2	4.750	4.750	0.50	14.3
SAPIL-3	4.500	4.500	1.00	6.5
SAPIL-4	4.000	4.000	2.00	1.6
SAPIL-5^d	4.875	4.875	0.25	14.4
SAPIL-6^e	4.875	4.875	0.25	27.4

Fig. 1. 13C solid-state magic angle spin NMR spectra of SAPIL-1 (a), SAPIL-2 (b), SAPIL-3 (c), SAPIL-4 (d), SAPIL-5 (e), and 13C NMR spectra of 1-vinyl-3-(3-sulfopropyl)imidazolium (VSIm) and sodium p-styrenesulfonate (NaSS) (dimethyl sulfoxide (DMSO)-d6).

Fig. 2. (a) XPS profiles of SAPIL-1 precursor and SAPIL-1; (b) TG curves of SAPIL-1-5 and Amberlite IR-120(H); (c) 31P solid-state magic angle spinning NMR spectra of TMPO chemically adsorbed on SAPIL-1 and H-ZSM-5 (Si/Al = 25). The asterisks denote spinning sidebands. The peaks at δ ≈ 43 and 33 belonged to the crystalline and physiosorbed TMPO, respectively [36].

Fig. 3. (a) SEM image of dried SAPIL-1; cryogenic SEM images of fully swollen SAPIL-1 in water sublimated for 5 min (b) and 30 min (c); (d) magnified image of area marked in (c).

Fig. 4. Schematic illustration of swelling-induced self-assembly process of SAPILs in water.

Table 2 Hydrolysis of cyclohexyl acetate catalyzed using various catalysts.a


Entry	Catalyst	Type	Acid concentration ^b(mmol/g)	Conversion ^c (%)	Selectivity ^d (%)
1	—	—	—	1.4	100
2	SAPIL-1	Hetero	1.95	81.9	98.3
3	SAPIL-2	Hetero	1.59	70.0	98.7
4	SAPIL-3	Hetero	1.12	62.9	98.9
5	SAPIL-5	Hetero	1.99	72.9	98.5
6	SAPIL-6	Hetero	2.03	81.5	98.7
7	Amberlite IR-120(H)	Hetero	4.60	28.5	96.8
8 ^e	H-ZSM-5	Hetero	0.86	49.3	36.3
9	[VSIm]HSO₄	Homo	6.23	47.1	99.2
10 ^f	H₂SO₄	Homo	20.39	46.2	98.9
11	p-TsOH	Homo	5.25	69.4	98.4

Fig. 5. Catalytic kinetics of various catalysts for the hydrolysis of cyclohexyl acetate. Reaction conditions: 10 mmol cyclohexyl acetate, 250 mmol H2O, 0.4 mmol catalyst, 100 °C, 1 bar N2.

Fig. 6. Catalytic activity of various catalysts for the hydrolysis of cyclohexyl propionate, cyclohexyl butyrate, and phenyl acetate. Reaction conditions: 10 mmol ester, 250 mmol H2O, 0.4 mmol catalyst, 100 °C, 7 h, 1 bar N2.

Fig. 7. (a) Concentration of cyclohexyl acetate in the aqueous phase of the simulated reaction mixtures. (b) Cyclohexyl acetate-to-cyclohexanol molar ratio in the aqueous phase of the simulated reaction mixtures. (c) Contact angles of (i) cyclohexyl acetate and (ii) cyclohexanol on the surface of SAPIL-1. Mixture-10%: cyclohexyl acetate (9 mmol), H2O (249 mmol), cyclohexanol (1 mmol), acetic acid (1 mmol); Mixture-30%: cyclohexyl acetate (7 mmol), H2O (247 mmol), cyclohexanol (3 mmol), acetic acid (3 mmol); Mixture-50%: cyclohexyl acetate (5 mmol), H2O (245 mmol), cyclohexanol (5 mmol), acetic acid (5 mmol); Mixture-70%: cyclohexyl acetate (3 mmol), H2O (243 mmol), cyclohexanol (7 mmol), acetic acid (7 mmol); Mixture-90%: cyclohexyl acetate (1 mmol), H2O (241 mmol), cyclohexanol (9 mmol), acetic acid (9 mmol); SAPIL-1 (0.102 g, 0.2 mmol); p-TsOH (0.038 g, 0.2 mmol).

Fig. 8. Catalytic reusability of SAPIL-1 for the hydrolysis of cyclohexyl acetate.

Fig. 9. Direct hydration of cyclohexene to cyclohexanol catalyzed by SAPIL-1 and p-TsOH. Reaction conditions: 20 mmol cyclohexene, 200 mmol H2O, 0.2 mmol (1 mol%) catalyst, 130 °C, 0.5 MPa N2, 1000 rpm.

Fig. 10. Hydration of ethylene oxide (EO) to ethylene glycol (EG) over various catalysts. Optimized reaction conditions (see Table S10): 50 mmol EO, 500 mmol H2O, 0.06 mmol (0.12 mol%) catalyst, 100 °C, 0.5 h, 1.0 MPa N2.

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