Acta Phys. -Chim. Sin. ›› 2019, Vol. 35 ›› Issue (3): 299-306.doi: 10.3866/PKU.WHXB201804172

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Removal of Methyl Orange from Aqueous Solutions by a Novel Hyper-Cross-Linked Aromatic Triazine Porous Polymer

Yan HE1,2,*(),Hao LI1,Li ZHOU2,Ting XU2,Changjun PENG2,Honglai LIU2,*()   

  1. 1 Jiangxi Province Key Laboratory of Polymer Micro/Nano Manufacturing and Devices, School of Chemistry, Biology and Materials Science, East China University of Technology, Nanchang 330013, P, R. China
    2 Key Laboratory for Advanced Materials, Department of Chemistry, East China University of Science and Technology, Shanghai 200237, P. R. China
  • Received:2018-03-15 Published:2018-08-28
  • Contact: Yan HE,Honglai LIU;
  • Supported by:
    the National Natural Science Foundation of China(21476070);the National Natural Science Foundation of China(21776069);the National Key Basic Research Program of China(2015CB251401)


Organic dyes, especially the harmful cationic dye methyl orange (MO), are emerging pollutants. The development of new materials for their efficient adsorption and removal is thus of great significance. Porous organic polymers (POPs) such as hyper-cross-linked polymers, covalent organic frameworks, conjugated microporous polymers, and polymers with intrinsic microporosity are a new class of materials constructed from organic molecular building blocks. To design POPs both with good porosity and task-specific functionalization is still a critical challenge. In this study, we have demonstrated a simple one-step method for the synthesis of the hyper-cross-linked aromatic triazine porous polymer (HAPP) via the Friedel-Crafts reaction. The resultant porous polymer was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, elemental analysis (EA), thermo-gravimetric analysis (TGA), solid-state 13C nuclear magnetic resonance (13C NMR), and nitrogen adsorption-desorption isotherms. The results show that HAPP is a rough, irregular morphology, porous organic polymer that is amorphous in nature. The novel polymer showed high Brunauer-Emmett-Teller surface area (of up to 104.36 m2∙g−1), porosity, and physicochemical stability. Owing to the presence of N heteroatom pore surfaces in the network, the material exhibited a maximum adsorption capacity of 249.3 mg∙g−1 for MO from aqueous solutions at room temperature. This is higher than that of some reported porous materials under the same conditions. To explain this phenomenon more clearly, theoretical quantum calculations were performed via the DFT method using Gaussian 09 software and Multiwfn version 3.4.1. It is performed to analyze the properties and electrostatic potential (ESP) of the HAPP monomer and MO. The results indicated that the N heteroatom of HAPP can easily develop strong interactions with MO, supporting the efficient adsorption of MO. The parameters studied include the physical and chemical properties of adsorption, pH, contact time, and initial concentrations. The percentage of MO removal increased as the pH was increased from 2 to 4. The optimum pH required for maximum adsorption was found to be 5.6. Adsorption kinetics data were modeled using the pseudo-first-order and pseudo-second-order models. The results indicate that the second-order model best describes the kinetic adsorption data. The adsorption isotherms revealed a good fit with the Langmuir model. More importantly, the HAPP can be regenerated effectively and recycled at least five times without significant loss of adsorption capacity. Therefore, it is believed that HAPPs with hierarchical porous structures, high surface areas, and physicochemical stability are promising candidates for the purification and treatment of dyes in solution.

Key words: Hyper-cross-linked porous polymer, One-step, Adsorption, Methyl orange, Regeneration


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