双中心多孔聚合物作为多相催化剂实现CO2在温和条件下高效转化

doi:10.1016/S1872-2067(20)63679-8

催化学报 ›› 2021, Vol. 42 ›› Issue (4): 618-626.DOI: 10.1016/S1872-2067(20)63679-8

双中心多孔聚合物作为多相催化剂实现CO₂在温和条件下高效转化

戴志锋^a, 唐永铨^b, 张飞^d, 熊玉兵^a^,^$(), 王赛^b, 孙琦^c, 王亮^c, 孟祥举^b, 赵雷洪^e^,^#(), 肖丰收^b^,^c^,^*()

^a浙江理工大学理学院化学系, 浙江杭州310018
^b浙江大学化学系浙江省应用化学重点实验室, 浙江杭州310028
^c浙江大学化学工程与生物工程学院生物化工教育部重点实验室, 浙江杭州310028
^d江西师范大学化学化工学院高级材料研究所科学院应用化学研究所, 江西南昌3300965浙江师范大学生化学院, 先进催化材料教育部重点实验室, 浙江金华321004

收稿日期:2020-05-24 接受日期:2020-07-11 出版日期:2021-04-18 发布日期:2021-01-22
通讯作者: 熊玉兵,赵雷洪,肖丰收
基金资助:
国家自然科学基金(21902145);浙江理工大学科研启动基金(18062303-Y)

Combination of binary active sites into heterogeneous porous polymer catalysts for efficient transformation of CO₂ under mild conditions

Zhifeng Dai^a, Yongquan Tang^b, Fei Zhang^d, Yubing Xiong^a^,^$(), Sai Wang^b, Qi Sun^c, Liang Wang^c, Xiangju Meng^b, Leihong Zhao^e^,^#(), Feng-Shou Xiao^b^,^c^,^*()

^aDepartment of Chemistry, College of Science, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China
^bKey Laboratory of Applied Chemistry of Zhejiang Province and Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
^cKey Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^dInstitute of Advanced Materials, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, Jiangxi, China

Received:2020-05-24 Accepted:2020-07-11 Online:2021-04-18 Published:2021-01-22
Contact: Yubing Xiong,Leihong Zhao,Feng-Shou Xiao
About author:^$E-mail: yubing_xiong@163.com
^#E-mail: zlh@zjnu.cn;
^*Tel: +86-571-88273282; E-mail: fsxiao@zju.edu.cn;
Supported by:
National Natural Science Foundation of China(21902145);Scientific Research Foundation of Zhejiang Sci-Tech University(18062303-Y)

摘要/Abstract

摘要：

由于对化石燃料的高度依赖和二氧化碳(CO₂)的过度排放, 大气中CO₂浓度从280 ppm上升到400 ppm左右, 导致全球变暖和其他气候问题. 在这种情况下, 如何有效降低空气中的CO₂浓度成为近年来最迫切的研究领域之一. 另一方面, 作为一种无毒、廉价且丰富的C1资源, CO₂也可以转化为各种高附加值的工业产品, 如甲酸、一氧化碳、甲烷、甲醇以及碳酸酯等. 其中CO₂与环氧化物转化生成环碳酸酯的环加成反应具有良好原子经济性, 在近年来引起了人们的广泛关注. 尽管已有多种多相和均相催化剂应用于该反应, 但已有的催化剂特别是多相催化剂往往具有反应条件苛刻、催化剂易损失以及需要可溶性的共催化剂等缺点, 从而限制了它们的进一步实际应用. 因此, 发展多相催化剂实现在温和和无共催化剂条件下的CO₂环加成转化仍是一个挑战.
本文通过自由基共聚的方法, 以乙烯基功能化的金属卟啉和季膦盐作为单体制备了一种新型多孔有机聚合物(POP-PBnCl-TPPMg-x). 考虑到金属卟啉和季膦盐常作为CO₂环加成反应中的Lewis酸和Lewis碱活性中心, 我们通过自由基共聚实现了这两种活性中心在分子水平上的结合与协同. 所得的催化剂的组成和结构通过固体核磁、X射线光电子能谱、氮气吸附、扫描电子显微镜、透射式电子显微镜等手段进行了表征. 值得指出的是, 所得多相催化剂具有良好的CO₂吸附与富集效应, 十分有利于CO₂的催化转化. 我们以温和(40 °C和1 atm CO₂)并没有任何无可溶性共催化剂存在条件下, 进行CO₂与环氧化物的环加成作为探针反应, 测试了不同催化剂的催化活性. 以催化剂POP-PBnCl-TPPMg-12为例, 其催化活性远超过单组分的POP-PBnCl和POP-TPPMg多相催化剂, 也超过了二者机械混合的POP-PBnCl+POP-TPPMg-12催化剂, 接近均相催化剂PBnCl+TPPMg-12的水平. 这表明通过共聚合方法所得到的催化剂可以实现Lewis酸和Lewis碱两种活性中心的分子水平的结合. 本文进一步研究了多相催化剂POP-PBnCl-TPPMg-12和均相催化剂PBnCl+TPPMg-12在低浓度CO₂(15% N₂ v/v, 工业废气中CO₂的浓度)条件下的催化活性, 发现在该条件下多相催化剂表现出比均相催化剂更为优异的催化转化性能, 且展现出良好的稳定性和循环使用性能, 在循环使用5次后仍无明显的活性损失. 该催化剂所具有的多相特点和优良的催化性能, 因而有望成为实现工业CO₂脱除并转化成高附加值产品的潜在高效催化剂.

关键词: 共聚, 多孔有机聚合物, 双活性中心, CO₂固定, 多相催化

Abstract:

The transformation of CO₂ into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention. On one hand, though many heterogeneous catalysts have been developed for this reaction, they typically suffer from disadvantages such as the need for severe reaction conditions, catalyst loss, and large amounts of soluble co-catalysts. On the other hand, the development of heterogeneous catalysts featuring multiple and cooperative active sites, remains challenging and desirable. In this study, we prepared a series of porous organic catalysts (POP-PBnCl-TPPMg-x) via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios. The resulting materials contain both Lewis-acidic and Lewis-basic active sites. The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically, giving rise to excellent performance in the cycloaddition reaction of CO₂ with epoxides, under mild conditions (40 °C and 1 atm CO₂) in the absence of soluble co-catalysts. POP-PBnCl-TPPMg-12 can also efficiently fixate CO₂ under low-CO₂-concentration (15% v/v N₂) conditions representative of typical CO₂ compositions in industrial exhaust gases. More importantly, this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity. In view of their heterogeneous nature and excellent catalytic performance, the obtained catalysts are promising candidates for the transformation of industrially generated CO₂into high value-added chemicals.

Key words: Copolymerization, Porous organic polymers, Binary active sites, Carbon dioxide fixation, Heterogeneous catalysis

戴志锋, 唐永铨, 张飞, 熊玉兵, 王赛, 孙琦, 王亮, 孟祥举, 赵雷洪, 肖丰收. 双中心多孔聚合物作为多相催化剂实现CO₂在温和条件下高效转化[J]. 催化学报, 2021, 42(4): 618-626.

Zhifeng Dai, Yongquan Tang, Fei Zhang, Yubing Xiong, Sai Wang, Qi Sun, Liang Wang, Xiangju Meng, Leihong Zhao, Feng-Shou Xiao. Combination of binary active sites into heterogeneous porous polymer catalysts for efficient transformation of CO₂ under mild conditions[J]. Chinese Journal of Catalysis, 2021, 42(4): 618-626.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63679-8

https://www.cjcatal.com/CN/Y2021/V42/I4/618

图/表 8

Fig. 1. 13C (A) and 31P (B) solid state NMR spectra of POP-PBnCl-TPPMg-4.

Fig. 2. N2 sorption isotherms (A), pore size distribution (B), SEM image (C), and TEM image (D) of POP-PBnCl-TPPMg-4.

Fig. 3. CO2 sorption isotherms at different temperatures (A) and the isosteric heat (Qst) of CO2 adsorption (B) for POP-PBnCl-TPPMg-4.

Table 1 Catalytic performances of the various catalysts in the cycloaddition of CO2 with epichlorohydrin to form a cyclic carbonate.a

Entry	Catalyst	Temperature (°C)	Conversion ^b (%)	Selectivity^b (%)
1	POP-PBnCl-TPPMg-4	40	52.4	99.0
2	POP-PBnCl-TPPMg-12	40	89.3	94.3
3^c	PBnCl+TPPMg-12	40	98.0	99.0
4	POP-PBnCl	40	20.3	99.0
5	POP-TPPMg	40	< 1.0	99.0
6	POP-PBnCl+POP-TPPMg-12	40	20.8	99.0
7^d	POP-PBnCl-TPP-12	40	24.2	99.0
8	POP-PBnCl-TPPMg-12	50	> 99.0	96.2
9	POP-PBnCl-TPPMg-12	30	54.3	99.0
10	POP-PBnCl-TPPMg-10	40	81.3	99.0
11	POP-PBnCl-TPPMg-20	40	99.0	99.0
12	POP-PBnCl-TPPZn-12	40	82.0	99.0
13	POP-PPrBr-TPPMg-12	40	91.7	99.0

Fig. 4. Catalytic performance of the heterogeneous catalyst POP-PBnCl-TPPMg-12 (blue line) and the homogeneous catalyst PBnCl+TPPMg-12 (red line) in the cycloaddition of CO2 with epoxides under a low CO2 concentration (15% CO2 and 85% N2, v/v). Note: For the heterogeneous catalyst, 1 mL of CH3CN was used as the solvent, while the homogeneous catalysis was performed in solvent-free conditions. The solid and dotted lines represent the conversion and selectivity, respectively.

Table 2 Cycloaddition of CO2 with various substrates over the catalyst POP-PBnCl-TPPMg-12.a

Entry	T (°C)	Time (h)	Conversion^b (%)	Selectivity ^b (%)
1	40	48	80.6	99.0
2	40	48	47.8	99.0
3	80	48	90.1	99.0
4	80	48	74.6	99.0
5	80	72	57.8	99.0
6	80	72	28.3	99.0

Fig. 5. Recycling test of POP-PBnCl-TPPMg-12 in the cycloaddition of CO2 with epoxides.

Fig. 6. Schematic illustration of the synthesis of the POP-PBnCl-TPPMg-x catalysts.

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双中心多孔聚合物作为多相催化剂实现CO₂在温和条件下高效转化

Combination of binary active sites into heterogeneous porous polymer catalysts for efficient transformation of CO₂ under mild conditions

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