Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

doi:10.1007/s11783-019-1101-z

Front. Environ. Sci. Eng.

2019, Vol. 13

Issue (2) : 18 https://doi.org/10.1007/s11783-019-1101-z

RESEARCH ARTICLE

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

Hang Zhang, Shuo Chen(

), Haiguang Zhang, Xinfei Fan, Cong Gao, Hongtao Yu, Xie Quan

Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China

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Abstract

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M).

Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction.

Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs.

C@M shows efficient catalytic degradation of pollutants over a wide pH range.

Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.

Keywords Heterogeneous Fenton-like catalysts MIL-88B-Fe CNTs Organic pollutants Mechanism

Corresponding Author(s): Shuo Chen

Issue Date: 25 January 2019

Cite this article:

Hang Zhang,Shuo Chen,Haiguang Zhang, et al. Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants[J]. Front. Environ. Sci. Eng., 2019, 13(2): 18.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1101-z
https://academic.hep.com.cn/fese/EN/Y2019/V13/I2/18

Fig.1 (a) XRD patterns for CNTs, C@M and MIL-88B-Fe; (b) FT-IR spectra for CNTs, C@M and MIL-88B-Fe; (c) C@M TEM image; (d) N₂ adsorption-desorption isotherms for MIL-88B-Fe and C@M.

Fig.2 (a) Degradation efficiency of phenol in different systems; (b) Kinetic constants of C@M and MIL-88B-Fe. Reaction Conditions: pH= 4, [H₂O₂] = 2.5 mmol/L, [catalyst] = 0.10 g/L, [phenol] = 25 mg/L, and T= 25℃.

Fig.3 (a) Degradation efficiency of phenol at different pH values (4–9); (b) Kinetic constants of C@M at different pH values. Other reaction Conditions: [H₂O₂] = 2.5 mmol/L, [catalyst] = 0.10 g/L, [phenol] = 25 mg/L, and T= 25℃.

Fig.4 (a) Degradation of phenol by C@M and homogenous Fenton catalyst with the same Fe content in ultrapure water without pH adjustment. Reaction conditions: [H₂O₂] = 2.5 mmol/L, [catalyst] = 0.1 g/L, [pollutants] = 25 mg/L, pH= 6.3 and T= 25℃. (b) Degradation of 2,4-DCP, SMZ and BPA. Reaction conditions: [H₂O₂] = 2.5 mmol/L, [catalyst] = 0.10 g/L, [pollutants] = 25 mg/L, pH= 4 and T= 25℃.

Fig.5 Reusability of C@M in Fenton-like reaction. Reaction conditions: pH= 4, [H₂O₂] = 2.5 mmol/L, [catalyst] = 0.10 g/L, [phenol] = 25 mg/L, and T= 25℃.

Fig.6 ESR spectra of DMPO-radical adducts in different reaction systems.

Fig.7 Fe2p XPS survey spectra of (a) MIL-88B-Fe, (b) C@M1, (c) C@M2, (d) C@M3 and (e) C@M4 before the reaction.

Tab.1 The Fe(II)/Fe(II)+Fe(III) ratio in different catalysts before the reaction

Tab.2 The Fe(II)/Fe(II)+Fe(III) ratio in C@M and MIL-88B-Fe during phenol degradation

Fig.8 Degradation of phenol by C@M-40℃, C@M-60℃ and C@M-80℃. Reaction Conditions: pH= 4, [H₂O₂] = 2.5 mmol/L, [catalyst] = 0.10 g/L, [phenol] = 25 mg/L, and T= 25℃.

Fig.9 Scheme 1 The comparison chart of reaction mechanism for C@M and MIL-88B-Fe.

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