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. 2022 Jul 29;14(15):3096.
doi: 10.3390/polym14153096.

β-Ketoenamine Covalent Organic Frameworks-Effects of Functionalization on Pollutant Adsorption

Tiago F Machado  1 , Filipa A Santos  1 , Rui F P Pereira  2 , Verónica de Zea Bermudez  3 , Artur J M Valente  1 , M Elisa Silva Serra  1 , Dina Murtinho  1
Affiliations

β-Ketoenamine Covalent Organic Frameworks-Effects of Functionalization on Pollutant Adsorption

Tiago F Machado et al. Polymers (Basel). .

Abstract

Water pollution due to global economic activity is one of the greatest environmental concerns, and many efforts are currently being made toward developing materials capable of selectively and efficiently removing pollutants and contaminants. A series of β-ketoenamine covalent organic frameworks (COFs) have been synthesized, by reacting 1,3,5-triformylphloroglucinol (TFP) with different C2-functionalized and nonfunctionalized diamines, in order to evaluate the influence of wall functionalization and pore size on the adsorption capacity toward dye and heavy metal pollutants. The obtained COFs were characterized by different techniques. The adsorption of methylene blue (MB), which was used as a model for the adsorption of pharmaceuticals and dyes, was initially evaluated. Adsorption studies showed that -NO2 and -SO3H functional groups were favorable for MB adsorption, with TpBd(SO3H)2-COF [100%], prepared between TFP and 4,4'-diamine- [1,1'-biphenyl]-2,2'-disulfonic acid, achieving the highest adsorption capacity (166 ± 13 mg g-1). The adsorption of anionic pollutants was less effective and decreased, in general, with the increase in -SO3H and -NO2 group content. The effect of ionic interactions on the COF performance was further assessed by carrying out adsorption experiments involving metal ions. Isotherms showed that nonfunctionalized and functionalized COFs were better described by the Langmuir and Freundlich sorption models, respectively, confirming the influence of functionalization on surface heterogeneity. Sorption kinetics experiments were better adjusted according to a second-order rate equation, confirming the existence of surface chemical interactions in the adsorption process. These results confirm the influence of selective COF functionalization on adsorption processes and the role of functional groups on the adsorption selectivity, thus clearly demonstrating the potential of this new class of materials in the efficient and selective capture and removal of pollutants in aqueous solutions.

Keywords: adsorption; covalent organic frameworks; heavy metals; methyl orange; methylene blue; β-ketoenamine.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Scheme of the TFP-based β-ketoenamine COF syntheses (a), schematic structure of resulting 2D COF layer (b), and structures of the dyes used in adsorption studies (c).
Figure 2
Figure 2
FTIR spectra of (a) TpPa-COF (black) and corresponding monomers TFP (purple) and Pa (blue); (b) TpPa-COF (red), TpBd-COF (brown), and TpBba-COF (orange).
Figure 3
Figure 3
Thermograms (solid) and dTG (dashed) of TpPa-COF (red), TpBd-COF (brown), and TpBba-COF (orange).
Figure 4
Figure 4
N2 sorption isotherms for (a) TpPa-COF (red) and TpBba-COF (orange), and (b) TpBd-COF (brown).
Figure 5
Figure 5
XRD patterns for TpPa-COF (black), TpBd-COF (blue), and TpBba-COF (red).
Figure 6
Figure 6
SEM images of TpPa-COF (a), TpBba-COF (b), and TpBd-COF (c) (×1500).
Figure 7
Figure 7
Removal efficiencies for the adsorption of MB (blue) and MO (orange) onto TpPa-COF, TpBba-COF, and TpBd-COF. Initial concentration of dyes: 20 ppm; mass of adsorbent: 4 mg.
Figure 8
Figure 8
SEM images of (a1,a2) TpPa-COF, (b1,b2) TpBba-COF, and (c1,c2) TpBd-COF before (1) and after (2) MB adsorption (×5000).
Figure 9
Figure 9
MB sorption isotherms (a) fitted to the Freundlich sorption model, and kinetics (b), fitted to the pseudo-second-order model, for TpPa-COF (red), TpBba-COF (orange), and TpBd-COF (brown).
Figure 10
Figure 10
FTIR spectra of Bd(NO2)2 (light blue), TpBd(NO2)2-COF [100%] (dark blue), Bd(SO3H)2 (light green), and TpBd(SO3H)2-COF [100%] (dark green).
Figure 11
Figure 11
Thermograms (solid) and dTG (dashed) of (a) TpBd-COF (brown), TpBd(NO2)2-COF [50%] (light blue), and TpBd(NO2)2-COF [100%] (dark blue); (b) TpBd-COF (brown), TpBd(SO3H)2-COF [50%] (light green), and TpBd(SO3H)2-COF [100%] (dark green).
Figure 12
Figure 12
Removal efficiencies for the adsorption of MB (blue) and MO (orange) onto functionalized TpBd-COF materials. Initial concentration of dyes: 20 ppm; mass of adsorbent: 4 mg.
Figure 13
Figure 13
MB sorption isotherms (a), fitted to the Freundlich sorption model, and kinetics (b), fitted to the pseudo-second-order model, for functionalized COFs.
Figure 14
Figure 14
Removal efficiencies of Cu(II), Pb(II), Ni(II), and Cd(II) by functionalized TpBd COFs. Initial metal ion concentrations: 5 ppm at pH 4.
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