Highly Stable Fluorine Containing Hierarchical Porous Covalent Organic Framework†

doi:10.7503/cjcu20180190

Abstract

Abstract:

Covalent organic frameworks(COFs) are an emerging class of crystalline and porous polymers synthesized by condensation reactions of organic building blocks linked through strong covalent bonds. How-ever, constructing dual-pore COFs with applicative building blocks were faced with enormous challenges due to the complicated topological structures formed through the limited strategies. Herein we describe the design and synthesis of a new dual-pore COF with a hexagram-like structure, named ETTA-TFA-COF, synthesized by linking a D_2h symmetric monomer and a C₂ symmetric monomer which leading the formation of dual-pore structure. The structure of the ETTA-TFA-COF was confirmed by theoretical simulation, powder X-ray diffraction(PXRD) investigation, nitrogen adsorption-desorption study, and FTIR spectra analysis. In the meantime, ETTA-TFA-COF material exhibit excellent stability in alkaline solution compared to COF materials of similar structure but without fluorine atoms.

Key words: Covalent organic frameworks, Fluorine containing hierarchical porous material, Crystal structure, Selective adsorption

CLC Number:

O611.4

TrendMD:

CHEN Qidan, TANG Junjie, FANG Qianrong. Highly Stable Fluorine Containing Hierarchical Porous Covalent Organic Framework^†[J]. Chem. J. Chinese Universities, 2018, 39(11): 2357.

Figures/Tables 8

Scheme 1 Synthesis and schematic representation of the simulated structure of ETTA-TFA-COFC: gray; N: blue; F: turquoise; H atoms are omitted for clarity.

Fig.1 Possible structures modelling predicted by accelrys Material Studio 7.0 software package (A) AA-H structure; (B) AA-O structure; (C) AB-H structure; (D) AB-O structure.C: gray, N: blue, F: turquoise; H atoms are omitted for clarity.

Fig.2 PXRD patterns of ETTA-TFA-COFa. Experimental; b. refined; c. diffe-rence of plot between the experimental and refined PXRD patterns; d. simulated PXRD pattern for AA-H structure; e. AB-H structure; f. AA-O structure; g. AB-O structure. Inset: detailed patterns for experimental(red) and simulated AA-H structure.

Fig.3 FTIR spectra of ETTA-TFA-COF(a), ETTA(b) and TFA(c)

Fig.4 TGA curve of ETTA-TFA-COF

Fig.5 SEM(A) and TEM(B) images of ETTA-TFA-COF

Fig.6 N2 adsorption-desorption isotherms(A) and pore-size distribution(B) of ETTA-TFA-COFAdsorption and desorption points are represented by filled and empty symbols, respectively.

Fig.7 XRD patterns of ETTA-PA-COF(A) and ETTA-TFA-COF(B) after treatment with different alkaline solutions for 24 ha. H2O; b. 3 mol/L NaOH solution; c. 6 mol/L NaOH solution; d. 9 mol/L NaOH solution.

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