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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63679-8

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

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

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