Facile synthesis of dual-functionalized microporous organic network for efficient removal of cationic dyes from water
Graphical abstract
Introduction
Water pollution has received increase attention due to the safety and scarcity of drinking water [1,2]. According to the World Bank report, the water-soluble organic dyes are considered to be the main contributors in water contamination [3]. The abuse and illegal discharge of organic dyes have caused serious environmental pollution and threat for human beings and aquatic life because the organic dyes are usually highly toxic, mutagenic, carcinogenic and hard to biodegrade [[4], [5], [6]]. Therefore, development of efficient and convenient methods for the removal and elimination of organic dyes from water are of extremely significant for environmental protection and drinking water safety [[7], [8], [9]].
The adsorption has been proven to be an attractive strategy for the elimination of organic dyes from water because of its high efficiency and simplicity [10]. The adsorbents play the dominant roles either for the selectivity or for the efficiency during the adsorption of organic dyes. The rational design and synthesis of efficient adsorbents to remove organic dyes from water have become an emergent and challenging topic. Until now, porous materials such as carbon nanotubes [11], layered double hydroxide [12], yolk-shell magnetic porous organic nanospheres [13], lignocellulose gels [14], magnetic grapheme oxide [15], polydopamine nanoparticles [16], metal-organic frameworks (MOFs) [[17], [18], [19], [20]], covalent-organic framework [21], MWCNT/alumina composite [22] and silsesquioxane-based hybrid porous polymers [[23], [24], [25], [26]] have been explored as advanced sorbents for efficient adsorption and removal of organic dyes. Development of novel adsorbents with large adsorption capacity and fast adsorption kinetics is still quite desirable for the removal and elimination of organic dyes from water.
Microporous organic networks (MONs), constructed via the Sonogashira coupling of alkynes and arylhalides, are a recent class of functional porous materials [[27], [28], [29]]. The good solvent and thermal stabilities, large surface area, designable structures and easy loading on other matrix made MONs potential in diverse areas and as advanced adsorbents for the efficient adsorption and removal of hazardous pollutants from water [[30], [31], [32], [33], [34]]. Aromatic benzene rings and ionic functional groups are usually included in organic dyes’ structures [[4], [5], [6]]. The π-π, hydrophobic, hydrogen bonding, metal coordination and electrostatic interactions are the possible adsorption mechanisms for the adsorption and removal of organic dyes from water [[12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26]]. Taking some of these factors into account when designing or modifying the adsorbents would largely improve their removal efficiency for organic dyes.
MONs with conjugate networks may possess good hydrophobic and π-π interactions for organic dyes [35]. Incorporation of hydrogen bonding sites or ionic function groups within MONs' networks would be a feasible way to improve their removal efficiency for organic dyes or hazardous pollutants [[36], [37], [38]]. For example, Liu et al. reported the post-synthesis of a pyrimidine modified MONs for improving the adsorption efficiency of anionic dyes from water [36]. Our group also showed the fabrication of hydroxyl and amino functionalized MONs for enhancing their removal efficiency for tetrabromobisphenol A [37,38]. The carboxyl groups were served as prior binding sites or groups to cationic dyes [19,20]. The carboxyl-containing porous materials such as MOFs and resins have been explored for the efficient adsorption and removal of cationic dyes [19,20,39]. Therefore, introduction of carboxyl groups along with hydrophobic sites into MONs’ networks may largely enhance their adsorption kinetic and removal efficiency for cationic organic dyes. However, the synthesis of carboxyl enriched MONs for cationic dyes removal has not been reported so far, not to mention the fabrication and application of dual-functionalized MONs for cationic dyes. Anhydride hydrolysis is a typical and commonly used reaction to prepare target acid or carboxyl functionalized materials.
Herein, we report the facile synthesis of a novel dual-functionalized MON (MON-4COOH) for efficient removal of cationic dyes from water (Fig. 1). The naphthalene-contained and carboxyl-enriched MON-4COOH was easily synthesized using 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride (DBTD) as the starting monomer. The anhydride groups within the DBTD can be hydrolyzed to provide multi-carboxyl groups within MON-4COOH under the basic synthesis condition to enhance the adsorption kinetics and removal efficiency for cationic dyes via electrostatic attraction and hydrogen bonding interaction. In addition, the naphthylene groups on networks can further enhance the π-π and hydrophobic interactions of MON-4COOH to the aromatic organic dyes. Based on the above predesigned interaction sites within the networks, the MON-4COOH gave fast adsorption kinetics and large adsorption capacities for three model cationic dyes methylene blue (MB), malachite green (MG) and crystal violet (CV), underling the great potential of MON-4COOH for the removal of cationic dyes and environmental pollutants from water.
Section snippets
Chemicals and reagents
All chemicals and reagents used were at least of analytical grade. Bis(triphenylphosphine) palladium dichloride (Pd(Pph3)2Cl2, 98%), DBTD (98%) and 2,6-dibromonaphthalene (98%) were obtained from TCI Co., Ltd. (Shanghai, China). Tetrakis(4-ethynylphenyl)methane (97%) was bought from Tongchuangyuan Pharmaceutical Technology Co. (Chengdu, China). Copper(I) iodide (CuI, 99.5%) was supplied by Aladdin Chemistry Co., Ltd. (Shanghai, China). Methylene blue (MB, 80%), malachite green (MG, 98%),
Characterization
The elemental analysis, solid 13C NMR, TGA, FT-IR, Raman spectrum, N2 adsorption-desorption experiments, FE-SEM, Zeta potential and water contact angle evaluations were used to characterize the obtained MON-4COOH (Fig. 2; Figs. S1–S2 and Table S1). The chemical shifts of solid 13C NMR at 120–150, and 60–95 ppm were ascribed to the signals of benzyl carbon, aromatic ring and internal alkyne on MON-4COOH, respectively (Fig. 2a) [35]. The chemical shift at 150–170 ppm was assigned to the
Conclusions
In summary, we have reported a convenient and facile anhydride hydrolysis strategy to synthesize a novel dual-functionalized MON-4COOH with enriched naphthalene and carboxyl groups for efficient removal of cationic dyes from water. The multiple and abundant interaction sites within MON-4COOH's networks led to the fast kinetic and remarkable adsorption capacity for cationic dyes. The good flow-through water treatment ability also made MON-4COOH highly potential for the remediation of cationic
CRediT authorship contribution statement
Xue Li: Conceptualization, Methodology, Investigation, Writing - original draft. Yuan-Yuan Cui: Investigation. Ying-Jun Chen: Validation. Cheng-Xiong Yang: Conceptualization, Resources, Funding acquisition, Supervision, Project administration, Writing - review & editing. Xiu-Ping Yan: Supervision.
Declarations of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the National Key Research and Development Program of China (2018YFC1602401), the National Natural Science Foundation of China (21777074), the Tianjin Natural Science Foundation (18JCQNJC05700), and the Fundamental Research Funds for the Central Universities.
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