A New Covalent Organic Framework Modified with Sulfonic Acid for CO2 Uptake and Selective Dye Adsorption

doi:10.6023/A21100454

Abstract

Environmental pollution is one of the most severe problems facing the earth today, including water pollution and the greenhouse effect caused by the indiscriminate discharge of organic dyes and abundant carbon dioxide emissions (CO₂), respectively. Therefore, removing dyes from water and eliminating CO₂ in the atmosphere is an urgent issue that needs to be solved. Among them, with low cost and high adsorption efficiency, porous materials have become one of the most common materials to adsorb organic dyes and uptake CO₂. Covalent organic frameworks (COFs), as a burgeoning class of crystalline porous polymers, present a promising application potential in many areas, such as gas adsorption and separation, heterogeneous catalysis, semiconductors and sensors due to their regular pores, modifiable frameworks, extensive specific areas and excellent stability. Especially the introduction of the functional groups to the skeleton of COFs provides abundant active sites to adsorb specific dyes and uptake gases. Inspired by this, we report a microporous COF (JUC-603, JUC=Jilin University China) decorated with sulfonic acid group. This COF was successfully synthesized through β-ketoenamine based Michael addition-elimination reaction of 1,3,5-tris(3-dimethylamino-1-oxoprop-2-en-yl)benzene (TDOEB) and p-phenylenediamine (PPDA). A series of characterizations proved that JUC-603 had high crystallinity, opening microporous pore and excellent stability. Nitrogen adsorption-desorption isotherm revealed a high Brunauer-Emmett-Teller (BET) surface area (774 m²/g) and large pore size (1.6 nm). Moreover, we studied the adsorption of JUC-603 on dyes from aqueous solutions by ultraviolet- visible spectrophotometry and the uptake capacity through CO₂ adsorption-desorption. These results showed that JUC-603 could selectively adsorb cationic dyes such as crystal violet and methylene blue as well as uptake CO₂ effectively (52 cm³/g at 273 K and 0.1 MPa). The ideal performance was attributed to the modulation of active sulfonic acid sites on the framework of JUC-603. This research thus indicates that the COF as a promising functionalized porous material has great potential in environmental remediation.

Key words: porous material, covalent organic frameworks, dye adsorption, CO₂ uptake, Michael addition-elimination reaction

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Zitao Wang, Yaozu Liu, Yujie Wang, Qianrong Fang. A New Covalent Organic Framework Modified with Sulfonic Acid for CO₂ Uptake and Selective Dye Adsorption[J]. Acta Chimica Sinica, 2022, 80(1): 37-43.

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Fig. & Tab. 9

Scheme 1. Syntheses of 3-PD and JUC-603

Figure 1. (a) PXRD patterns and (b) structural representations of 3-PD; (c) PXRD patterns and (d) structural representations of JUC-603

Figure 2. (a) FT-IR spectra, (c) solid-state 13C NMR spectrum and (e) TGA curve of 3-PD; (b) FT-IR spectra, (d) solid-state 13C NMR spectrum and (f) TGA curve of JUC-603

Figure 3. PXRD patterns of JUC-603 after the treatment in a variety of organic solvents and acid (1.0 mol/L HCl) aqueous solution for 24 h

Figure 4. N2 adsorption-desorption isotherms of (a) 3-PD and (b) JUC-603; the pore-size distribution of (c) 3-PD and (d) JUC-603 estimated by nonlocal density functional theory (NLDFT)

COFs	CO₂吸收能力/(cm³•g^-1)
COF-1	51
COF-5	31
COF-103	38
TDCOF-5	47
DmaTph	37
RT-COF-1	44
3-PD	45
JUC-603	51.7

Table 1. The CO2 uptake ability of several common COFs

Figure 5. CO2 uptakes for 3-PD at (a) 298 K and (b) 273 K as well as JUC-603 at (c) 298 K and (d) 273 K

Figure 6. The standard UV-Vis curves of crystal violet (a) and methylene blue trihydrate (b); UV-Vis absorption spectra of crystal violet aqueous solution in the presence of (c) JUC-603 and (d) 3-PD; UV-Vis absorption spectra of methylene blue trihydrate aqueous solution in the presence of (e) JUC-603 and (f) 3-PD; comparison of (g) acid orange 10 and (h) fluorescein sodium adsorption between 3-PD and JUC-603 after 2 h

Figure 7. PXRD patterns of JUC-603 after adsorbing different dyes

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一种新型磺酸修饰的共价有机框架用于二氧化碳吸收和染料吸附

A New Covalent Organic Framework Modified with Sulfonic Acid for CO₂ Uptake and Selective Dye Adsorption

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