Facile Synthesis of Porous Organic Polymer/Chitosan Composites and the Removal Effect of Hg(Ⅱ)

SHEN Rujia; XU Naicen; SHI Lei; HUANG Haibo; CHEN Haiying; ZHANG Jing; SHEN Jialin; LI Hualing; CHEN Yali

doi:10.15898/j.ykcs.202211170219

Rock and Mineral Analysis > 2024 > 43(2): 289-301. > DOI: 10.15898/j.ykcs.202211170219

SHEN Rujia，XU Naicen，SHI Lei，et al. Facile Synthesis of Porous Organic Polymer/Chitosan Composites and the Removal Effect of Hg(Ⅱ)[J]. Rock and Mineral Analysis，2024，43（2）：289−301. DOI: 10.15898/j.ykcs.202211170219

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Facile Synthesis of Porous Organic Polymer/Chitosan Composites and the Removal Effect of Hg(Ⅱ)

SHEN Rujia^{1, 2,},
XU Naicen^{1, 2},
SHI Lei^{1, 2},
HUANG Haibo^{1, 2},
CHEN Haiying^{1, 2},
ZHANG Jing^{1, 2},
SHEN Jialin^{1, 2, ,},
LI Hualing^{1, 2, ,},
CHEN Yali^{2, 3}

1.
Nanjing Center, China Geological Survey; East China Geological Science and Technology Innovation Center, Nanjing 210016, China
2.
Huaihe River Basin Joint Laboratory of Natural Resources and Ecological Environment Science, Nanjing 210016, China
3.
Huaihe Valley Ecology and Environment Administration, Ministry of Ecology and Environment, Benbu 233060, China

More Information

Received Date: November 16, 2022
Revised Date: January 29, 2024
Accepted Date: February 06, 2024
Available Online: April 28, 2024

Abstract

HIGHLIGHTS
(1) Based on the Schiff base reaction, element-doped porous organic polymers can be synthesized quickly and easily by the mechanical grinding method.

(2) For TpTU@CS, the main mechanism of capturing Hg(Ⅱ) is the bonding between S and Hg in C=S and the coordination interaction between C−N and Hg(Ⅱ).

(3) In the range of pH=2−7, the adsorption properties of Hg(Ⅱ) are less affected by pH, and the three forms of Hg(Ⅱ) including Hg²⁺, Hg(OH)⁺ and Hg(OH)₂ are favorable for adsorption.

ABSTRACT

Specific porous structures and heteroatom-doped adsorbents have great importance in improving the adsorption performance of heavy metal ions. Traditional porous organic polymer materials are mostly synthesized in solvents in the form of powder, so it is significant to develop a highly efficient adsorption material and apply it to the adsorption and removal of Hg(Ⅱ). In the research, S-doped porous organic polymer (TpTU) and chitosan (CS) composites TpTU@CS were prepared by using 1,3,5-trialaldehyde phloroglucinol (Tp) and thiourea (TU) by a simple and rapid mechanical grinding method. The TpTU@CS composites were characterized by X-ray diffraction spectroscopy, N₂ adsorption-desorption, scanning electron microscope and Fourier transform infrared spectroscopy. Due to the introduction of the −C=S− group into the molecular network, the synthesized TpTU@CS has high adsorption selectivity and affinity for Hg(Ⅱ) in aqueous solution, with high adsorption capacity (249.21mg/g) and fast adsorption kinetics (10min). Through the characterization analysis, it is concluded that the main mechanism of trapping Hg(Ⅱ) by TpTU@CS is the bonding between S and Hg in C=S and the coordination interaction between C−N and Hg(Ⅱ). Meanwhile, the composite TpTU@CS has a high removal capacity (77.0%−100.0%) of Hg(Ⅱ) for both the actual samples and the marked samples. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202211170219.
- porous organic polymer,
- composite microsphere,
- mercury,
- structural characterization,
- adsorption property,
- X-ray photoelectron spectroscopy
BRIEF REPORT
Significance: Heavy metal pollution has caused great losses to national health and economic development. Mercury(Hg) is one of the most toxic heavy metal pollutants^[1]. It easily accumulates in the human body and can cause birth defects, brain damage and other diseases in humans and animals. Adsorption method is one of the more convenient and low-cost methods for Hg(Ⅱ) removal, but the adsorption capacity of traditional adsorbent materials is low, and ineffective in practical application. Therefore, it is crucial to develop new materials with high affinity and adsorption properties for Hg(Ⅱ). Porous organic polymers (POPs) are emerging materials. In recent years, POPs based adsorbents have been increasingly used to remove harmful substances^[2-3]. The inclusion of functional groups (e.g. −NH₄, −SH) in the synthesis of POPs adsorbents can enhance their affinity and selectivity for metal ions^[4-5]. However, POPs commonly direct synthesis by a bottom-up method using monomers containing hybrid elements, which has the disadvantage that functional groups can be damaged during the reaction process. In the research, based on the Schiff base reaction theory of tautomerism of enol-ketone, a novel C=S functionalized POPs material was developed by a green preparation method of mechanical grinding, which was then integrated into a microsphere with chitosan. The rich free −NH₂ and −OH functional groups in chitosan interacts with various organic groups to form a three-dimensional network with good stability. In addition, the highly ordered microporous/mesoporous structure of the novel materials is conducive to the diffusion of adsorbed substances and exposure of active sites, thus improving the mass transfer efficiency.

Methods: A S-doped porous organic polymer and chitosan composite material TpTU@CS was prepared by adopting green strategy. 34.2mg thiourea and 530.3mg p-toluenesulfonic acid were ground in agate mortar for 5min. After grinding evenly, 63.1mg 1,3,5-trialdehyde-resorcinol was added and grinding continued for 5−8min until even again. A small amount of water was added during grinding to give it a certain fluidity. The mixture was then transferred to the Teflon lining of the reactor and reacted at 140℃ for 12h. After the reaction, it was cleaned three times in turn with hot water, N,N-dimethylacetamide, hot water and acetone, and dried in vacuum for subsequent use, and the obtained material was named TpTU. The TpTU material 0.5g and chitosan 2.5g were added to 20mL 1% (V/V) acetic acid solution. After stirring for 3h, it was dropped into 1.0g/L NaOH solution, the obtained microspheres were washed with ultra-pure water until the pH becomes neutral, and then 10mL 25% glutaraldehyde solution was added. After storing for 3h, the microspheres were collected and washed with ultra-pure water several times. TpTU@CS is obtained by freeze-drying.

　　The specific surface area and pore size distribution were calculated using the nitrogen adsorption-desorption system based on Bruner-Emmett-Teller and Barrett-Joyner-Halenda methods. The nitrogen adsorption-desorption isotherm was collected at 77K and high purity nitrogen (>99.999%) was measured. Fourier transform infrared (FTIR) spectra of different samples were collected by infrared spectrometer with a resolution of 4cm^-1 and a range of 400−4000cm^-1. The crystal structure of the sample was analyzed by X-ray diffractometer. The surface morphology and elemental content of the samples were recorded by Merlin scanning electron microscopy and its energy dispersive fluorescence X-ray system (EDS). The composition and chemical state of the surface elements were studied by X-ray photoelectron spectroscopy (Al Kα radiation), with emphasis on the fine spectrum analysis of O, N, S and Hg.

Data and Results: The SEM shows that the synthetic material is a cluster of spheroidal particles with a rough surface (Fig.1). In the infrared spectra (Fig.2a), after the reaction of TU and Tp, the −NH₂ tensile vibration peak (1414cm^-1) of the original TU molecule almost disappears, and a new C−N bond peak is formed at 1286cm^-1, indicating that Tp and TU are successfully polymerized. The BET specific surface area of TpTU@CS is 82.138m²/g, and the porous structure of TpTU@CS is conducive to improving the mass transfer rate. A large specific surface area can increase the number of adsorption sites.

　　The adsorption experiments show that the adsorption pattern of Hg(Ⅱ) on TpTU@CS is more consistent with the Freundlich model, indicating that Hg(Ⅱ) is more consistent with non-uniform adsorption on TpTU@CS. The adsorption of Hg(Ⅱ) is more consistent with pseudo-first-order kinetics, which indicates that the diffusion step controls the adsorption. The synthesized TpTU@CS has higher adsorption selectivity and affinity for Hg(Ⅱ) in aqueous solution, with high adsorption capacity (249.21mg/g) and fast adsorption kinetics (10min). As shown in Table 2, this composite material TpTU@CS is successfully used to remove Hg(Ⅱ) from water, showing high removal capacity (77.0%−100.0%) for both actual water samples contaminated with low concentration of Hg(Ⅱ) and high concentration marked water samples. TpTU@CS material can achieve 100% removal rate of Hg(Ⅱ) aqueous solution within 10min, which can be attributed to its regular pore structure (13nm).

　　Through XPS characterization in Fig.5 and Fig.6, it is found that the chemical mechanism is mainly the bonding effect between S and Hg. The formation of a covalent bond ensures the excellent adsorption capacity of TpTU@CS for Hg(Ⅱ). The strong coordination of −S−Hg− is also confirmed by exploring the influence of pH on adsorption. Under the test conditions [5mg TpTU@CS in 5mL 10mg/L Hg(Ⅱ) at different pH values], and among all the pH values tested, TpTU@CS achieves 100% removal rate of Hg(Ⅱ), which proves that the three forms of Hg(Ⅱ) including Hg²⁺, Hg(OH)⁺ and Hg(OH)₂ are favorable for adsorption.

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References (40)

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