酸性聚离子液体溶胀诱导自组装形成类蜂窝状固体酸催化剂及其高效催化水解反应

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

催化学报 ›› 2021, Vol. 42 ›› Issue (2): 297-309.DOI: 10.1016/S1872-2067(20)63658-0

酸性聚离子液体溶胀诱导自组装形成类蜂窝状固体酸催化剂及其高效催化水解反应

陈必华^a, 丁桐^a, 邓熹^a, 王鑫^a, 张大卫^a^,^b, 马三罐^a, 张永亚^a, 倪兵^c, 高国华^a^,^*()

^a华东师范大学化学与分子工程学院, 上海市绿色化学与化工过程绿色化重点实验室, 上海200062, 中国
^b剑桥大学化学系, 剑桥 CB2 1EW, 英国
^c华东师范大学生命科学学院, 上海200241, 中国

收稿日期:2020-03-29 接受日期:2020-05-08 出版日期:2021-02-18 发布日期:2021-01-21
通讯作者: 高国华
基金资助:
国家自然科学基金(21773068);国家自然科学基金(21573072);国家自然科学基金(21811530273);国家重点研发计划(2017YFA0403102);上海市重点学科建设项目(B409)

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

Bihua Chen^a, Tong Ding^a, Xi Deng^a, Xin Wang^a, Dawei Zhang^a^,^b, Sanguan Ma^a, Yongya Zhang^a, Bing Ni^c, Guohua Gao^a^,^*()

^aShanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
^bDepartment of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.
^cSchool of Life Sciences, East China Normal University, Shanghai 200241, China

Received:2020-03-29 Accepted:2020-05-08 Online:2021-02-18 Published:2021-01-21
Contact: Guohua Gao
About author:^*Tel/Fax: +86-21-62233323; E-mail: ghgao@chem.ecnu.edu.cn
Supported by:
National Natural Science Foundation of China(21773068);National Natural Science Foundation of China(21573072);National Natural Science Foundation of China(21811530273);National Key Research and Development Program of China(2017YFA0403102);Shanghai Leading Academic Discipline Project(B409)

摘要/Abstract

摘要：

酸催化反应在化学工业中占据着十分重要的地位. 传统的液体酸催化剂催化性能优异, 但面临着能耗高, 腐蚀设备和环境污染严重等问题. 相比于传统的液体酸催化剂, 固体酸催化剂, 如分子筛和磺酸树脂等大大缓解了经济和环境方面的问题, 但也存在着催化活性差和易失活等缺陷. 酸性聚离子液体因其高密度的反应活性位点, 可设计调变的结构和酸性以及可循环利用等特性而成为一种新型的高效多相酸催化剂, 引起了广泛的研究兴趣. 然而, 当酸性聚离子液体用作催化剂时, 由于其酸中心不能充分地暴露在反应底物中, 使得它们的催化活性难以达到甚至超越均相催化剂的水平. 因此, 发展一种催化活性高于均相的酸性聚离子液体催化剂仍是一个巨大的挑战. 我们研究组发现在反应底物中溶胀的聚离子液体可作为一种准均相催化剂, 其催化活性与相应的均相离子液体相当, 这为提高多相催化剂的催化活性提供了一种新的策略.
本文报道了一种在水中溶胀且自组装成类蜂窝状网络结构的酸性聚离子液体催化剂, 该催化剂在水解和水合反应中表现出优异的催化性能, 其活性高于均相酸催化剂. 首先通过自由基聚合和酸化两步合成了一系列在水中高度溶胀的酸性聚离子液体(SAPIL-1-6). 以三甲基磷氧(TMPO)为探针分子, 用³¹P魔角旋转核磁共振(³¹P-TMPO NMR)对SAPILs的酸性进行了分析. 结果表明, SAPILs具有中等强度的单一酸性. 热重分析表明SAPILs拥有优异的热稳定性能(300-345 ºC), 显著地优于商用磺酸树脂Amberlite IR-120(H) (245 ºC). 扫描电镜和冷冻电镜表明, 当SAPILs在水中溶胀时, 无孔的结构会自发地形成微米级三维类蜂窝状网络结构. 这些类蜂窝状网络结构的酸性聚离子液体在催化乙酸环己酯水解制备环己醇中表现出卓越的催化性能, 其催化活性明显高于多相酸催化剂(Amberlite IR-120(H)和H-ZSM-5)和均相酸催化剂(硫酸, 对甲苯磺酸和均相酸性离子液体[VSIm]HSO₄). 通过气相色谱定量分析了在一系列模拟的反应体系中溶胀SAPIL-1内部和外部各组分的平衡浓度, 发现SAPIL-1内部乙酸环己酯的浓度和乙酸环己酯与环己醇的摩尔比分别是其外部的7.5-23.3倍和4.5-16.4倍, 这表明在反应过程中乙酸环己酯被大量富集. 此外, SAPILs在环己烯直接水合制备环己醇以及环氧乙烷水合制备乙二醇的反应中均表现出优异的催化性能. 值得说明的是, SAPILs具有很好的循环使用性能, 10次循环后催化活性无明显改变. 这些具有蜂窝状结构和对反应底物高富集SAPILs的成功合成及应用为开发高效的多相酸催化剂提供了一种新的思路.

关键词: 多相酸催化剂, 酸性聚离子液体, 溶胀, 三维类蜂窝状网络结构, 富集, 水解, 水合

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

陈必华, 丁桐, 邓熹, 王鑫, 张大卫, 马三罐, 张永亚, 倪兵, 高国华. 酸性聚离子液体溶胀诱导自组装形成类蜂窝状固体酸催化剂及其高效催化水解反应[J]. 催化学报, 2021, 42(2): 297-309.

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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图/表 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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酸性聚离子液体溶胀诱导自组装形成类蜂窝状固体酸催化剂及其高效催化水解反应

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

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