Synergistic Removal of Co-contamination by Heterogeneous Fenton System: Chemical Conversion, pH Effect and Mechanism Analysis

doi:10.6023/A19060203

Abstract

The chemical transformation of ZVI micro-surface and the degradation mechanism in the process of synergistic removal of copper ions and methylene blue pollutants by ZVI-Fenton system were studied systematically. The samples of ZVI, before and after reaction in the ZVI/H₂O₂ and ZVI/H₂O₂-Cu systems, were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and Fourier Transform infrared spectroscopy (FTIR) to research the changes of ZVI surface structure, Fe and Cu species’ chemical conversion. The results showed that the residual corrosion products on the surface of ZVI were more and the corrosion products were mainly Fe₃O₄ and Fe₂O₃ after reaction in the ZVI/H₂O₂ system. However, in the ZVI/H₂O₂-Cu system, the corrosion effect of ZVI was more significant, but the residual corrosion products of ZVI surface were less, and the proportion of Fe₃O₄ increased. In addition, the main reduction product of Cu ²⁺ was Cu ⁰, which was accompanied by the generation of CuO. Furthermore, the effects of pH on the removal of pollutants from the five systems (ZVI, ZVI-Cu, H₂O₂-Cu, ZVI/H₂O₂ and ZVI/H₂O₂-Cu) were compared and the changes in TCu and TFe concentrations under different pH conditions were monitored. The results indicated that the ZVI/H₂O₂-Cu system not only simultaneous effectively remove MB and TCu compared with other three systems, but also enlarged the effective pH range (pH=2.5~5.5) of ZVI-Fenton system. In addition, free radical capture experiments showed that hydroxyl radicals played an important role in the oxidative degradation of methylene blue, and 10 mmol/L tert-butanol could completely capture hydroxyl radicals in the system. Finally, the mechanism of synergistic removal of TCu and MB degradation by ZVI-Fenton system was revealed. The substitution reaction between ZVI and Cu ²⁺, the action of Cu ⁰ and ZVI galvanic cells, the acid corrosion effect, and the redox cycle of iron and copper together accelerate the degradation of MB by the system and promote the conversion of ZVI surface substances. This study provides a theoretical basis for collaborative treatment of industrial complex pollutants.

Key words: zero-valent iron powder, heterogeneous Fenton, cyclic catalysis, synergism, micro surface transformation

Cite this article

Yang, Bo, Zhang, Yongli. Synergistic Removal of Co-contamination by Heterogeneous Fenton System: Chemical Conversion, pH Effect and Mechanism Analysis[J]. Acta Chimica Sinica, 2019, 77(10): 1017-1023.

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Fig. & Tab. 8

Figure 1. SEM images and EDS spectra of ZVI: (a), (b) pristine ZVI; (c), (d) after reaction in ZVI/H2O2 system; (e), (f) after reaction in ZVI/H2O2-Cu system

Figure 2. XRD patterns of ZVI before and after reaction

Figure 3. XPS spectra of ZVI before and after reaction: (a) full-scan spectra; (b) Fe 2p in the ZVI/H2O2 system; (c) Cu 2p and (d) Fe 2p in the ZVI/H2O2-Cu system

Element (photo electro core level)	Peak position/eV		Assignment	Area	FWHM/eV
Element (photo electro core level)	ZVI/H₂O₂	ZVI/H₂O₂-Cu	Assignment	Area	FWHM/eV
Fe 2p	724.1		2p_1/2Fe₂O₃	5473.1	7.323
	716.7		Satellite of Fe₂O₃	1373.7	4.47
	712.1		2p_3/2Fe₂O₃	2281.4	2.333
	710.2		2p_3/2 Fe₃O₄	1825.9	1.539
		724.1	2p_1/2 Fe₂O₃	5264.5	9.995
		712.1	2p_3/2Fe₂O₃	1735.5	3013
		710.2	2p_3/2 Fe₃O₄	1584.5	1.707
Cu 2p	—	952.7	2p_1/2 CuO	128.8	1.745
	—	942.0	2p_3/2 CuO	160.1	2.025
	—	932.7	2p_3/2Cu⁰	794.2	2.808

Table 1. Chemical states of Fe, Cu elements and parameters

Figure 4. FTIR spectra of ZVI before and after reaction

Figure 5. The effect of initial pH on the ZVI/H2O2-Cu, ZVI/H2O2, ZVI-Cu, H2O2-Cu and ZVI system. (a) removal of MB; (b) removal of TCu; (c) concentration of TFe; (d) concentration changes of TFe and H2O2 in the ZVI system at pH=2.5

Figure 6. The effect of TBA concentration on the removal of MB

Figure 7. The mechanism for synergistic removal of TCu and MB by the ZVI/H2O2-Cu system

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