Citation: Sun Mengjia, Wu Tianyi, Li Tianyu, Guo Fengqiao, Tang Yang, Mo Hengliang, Yang Zhitao, Wan Pingyu. Research on High Performance Ammonium Removal Materials Based on δ-MnO2 Nanoplate Arrays Decorated Graphite Felt[J]. Acta Chimica Sinica, ;2018, 76(6): 467-474. doi: 10.6023/A18020069 shu

Research on High Performance Ammonium Removal Materials Based on δ-MnO2 Nanoplate Arrays Decorated Graphite Felt

  • Corresponding author: Wan Pingyu, pywan@mail.buct.edu.cn
  • Received Date: 10 February 2018
    Available Online: 3 June 2018

    Fund Project: Project supported by the National Natural Science Foundation of China (No. 21506010) and the Beijing Natural Science Foundation (No. 2182050)the Beijing Natural Science Foundation 2182050the National Natural Science Foundation of China 21506010

Figures(9)

  • We synthesized three kinds of MnO2 powder with different crystalline phases including α-MnO2 nanoflowers, β-MnO2 nanorods and δ-MnO2 micro-particles. The structure and morphology of prepared MnO2 were studied by XRD (X-ray diffraction), SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope) and XPS (X-ray photoelectron spectroscopy), systematically. Adsorption process was conducted in NH4Cl solution (40 mg·L-1 NH3-N) and actual water samples containing NH4+, Ca2+, Mg2+, K+ and Na+, respectively. The results demonstrate that δ-MnO2 with 7.2 Å interlayer spacing which is a little larger than the diameter of hydrated ammonium (6.62 Å) has high adsorption capacity; α-MnO2 with[2×2] tunnel of 4.6 Å has less adsorption capacity than that of δ-MnO2, and β-MnO2 whose[1×1] tunnel is just 1.89 Å, barely has adsorption capacity. Then MnO2NPs/GF (MnO2 nanoplates decorated graphite felt) was prepared via a facile in-situ redox process. Graphite felt (GF) was immersed in KMnO4 solution (4 g·L-1, pH=2) at 65℃ for 5 h to get MnO2NPs/GF. GF not only reacted as the reductant of KMnO4, but also acted as 3D framework to support the in-situ deposited MnO2NPs. MnO2NPs/GF shows high adsorption capacity (15 mg·g-1) and good selectivity (86.7%). In repetitive adsorption-desorption experiments, MnO2NPs/GF not only exhibits good stability after 20 cycles, but also decreases the concentration of NH3-N to as low as 1 mg·L-1. The thermodynamics experiment demonstrates that the adsorption isotherm fit well with Langmuir isotherm, and the adsorption process corresponds to the pseudo-second-order model. The excellent performance of MnO2NPs/GF is attributed to the following three aspects. Firstly, the 7.2 Å interlayer spacing of δ-MnO2 is suitable for the exchange-adsorption of NH4+. Secondly, the ultra-thin MnO2 nanoplate arrays, which vertically grow on the graphite felt substrate, provide fast path and convenient interface for ion exchange. Finally, the interlaced nanoplates with self-supported structure ensure its high stability. In a conclusion, MnO2NPs/GF has a bright future in the field of ammonium removal.
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