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Nano Research 2022, 15(3): 1973-1982 https://doi.org/10.1007/s12274-021-3848-3
Research Article | Issue | Published: 09 September 2021

Reinventing MoS2 Co-catalytic Fenton reaction: Oxygen-incorporation mediating surface superoxide radical generation

Show Author's Information Xianjun Tan,  Wenhui Ding,  Zhenying Jiang,  Linxiao Sun,  Yuxiong Huang( )
Environmental Science and New Energy Technology Research Center, Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China
Keywords:
reactive oxygen species (ROS), Co-catalytic Fenton reaction, MoS2 nanosheets , superoxide radical, antibiotics’ degradation
Topics:
Nanocatalysts
Cite this article:
Tan X, Ding W, Jiang Z, et al. Reinventing MoS2 Co-catalytic Fenton reaction: Oxygen-incorporation mediating surface superoxide radical generation. Nano Research, 2022, 15(3): 1973-1982. https://doi.org/10.1007/s12274-021-3848-3
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Abstract Full text About this article

To better understand the mechanisms of hydrogen peroxide (H2O2)’s decomposition and reactive oxygen species (ROS)’s formation on the catalyst’s surface is always a critical issue for the environmental application of Fenton/Fenton-like reaction. We here report a new approach to activate H2O2 in a co-catalytic Fenton system with oxygen incorporated MoS2, namely MoS2−xOx nanosheets. The MoS2−xOx nanosheets assisted co-catalytic Fenton system exhibited superior degradation activity of emerging antibiotic contaminants (e.g., sulfamethoxazole). Combining density functional theory (DFT) calculation and experimental investigation, we demonstrated that oxygen incorporation could improve the intrinsic conductivity of MoS2−xOx nanosheets and accelerate surface/interfacial charge transfer, which further leads to the efficacious activation of H2O2. Moreover, by tuning the oxygen proportion in MoS2−xOx nanosheets, we are able to modulate the generation of ROS and further direct the oriented-conversion of H2O2 to surface-bounded superoxide radical (·O2−surface). It sheds light on the generation and transformation of ROS in the engineered system (e.g., Fenton, Fenton-like reaction) for efficient degradation of persistent pollutants.


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About this article

Reinventing MoS2 Co-catalytic Fenton reaction: Oxygen-incorporation mediating surface superoxide radical generation

Show Author's information Xianjun Tan, Wenhui Ding, Zhenying Jiang, Linxiao Sun, Yuxiong Huang( )
Environmental Science and New Energy Technology Research Center, Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China

Abstract

To better understand the mechanisms of hydrogen peroxide (H2O2)’s decomposition and reactive oxygen species (ROS)’s formation on the catalyst’s surface is always a critical issue for the environmental application of Fenton/Fenton-like reaction. We here report a new approach to activate H2O2 in a co-catalytic Fenton system with oxygen incorporated MoS2, namely MoS2−xOx nanosheets. The MoS2−xOx nanosheets assisted co-catalytic Fenton system exhibited superior degradation activity of emerging antibiotic contaminants (e.g., sulfamethoxazole). Combining density functional theory (DFT) calculation and experimental investigation, we demonstrated that oxygen incorporation could improve the intrinsic conductivity of MoS2−xOx nanosheets and accelerate surface/interfacial charge transfer, which further leads to the efficacious activation of H2O2. Moreover, by tuning the oxygen proportion in MoS2−xOx nanosheets, we are able to modulate the generation of ROS and further direct the oriented-conversion of H2O2 to surface-bounded superoxide radical (·O2−surface). It sheds light on the generation and transformation of ROS in the engineered system (e.g., Fenton, Fenton-like reaction) for efficient degradation of persistent pollutants.

Keywords: reactive oxygen species (ROS), Co-catalytic Fenton reaction, MoS2 nanosheets , superoxide radical, antibiotics’ degradation

References(49)

1

Bokare, A. D.; Choi, W. Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes. J. Hazard. Mater. 2014, 275, 121–135.
DOI Google Scholar
2

Nosaka, Y.; Nosaka, A. Y. Generation and detection of reactive oxygen species in photocatalysis. Chem. Rev. 2017, 117, 11302–11336.
DOI Google Scholar
3

Fenton, H. J. H. LXXIII. —Oxidation of tartaric acid in presence of iron. J. Chem. Soc., Trans. 1894, 65, 899–910.
DOI Google Scholar
4

Zhu, Y. P.; Zhu, R. L.; Xi, Y. F.; Zhu, J. X.; Zhu, G. Q.; He, H. P. Strategies for enhancing the heterogeneous Fenton catalytic reactivity: A review. Appl. Catal. B: Environ. 2019, 255, 117739.
DOI Google Scholar
5

Yan, Q. Y.; Zhang, J. L.; Xing, M. Y. Cocatalytic Fenton reaction for pollutant control. Cell Rep. Phys. Sci. 2020, 1, 100149.
DOI Google Scholar
6

Zou, J.; Ma, J.; Chen, L. W.; Li, X. C.; Guan, Y. H.; Xie, P. C.; Pan, C. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine. Environ. Sci. Technol. 2013, 47, 11685–11691.
DOI Google Scholar
7

Hou, X. J.; Huang, X. P.; Ai, Z. H.; Zhao, J. C.; Zhang, L. Z. Ascorbic acid/Fe@Fe2O3: A highly efficient combined Fenton reagent to remove organic contaminants. J. Hazard. Mater. 2016, 310, 170–178.
DOI Google Scholar
8

Zhang, Y.; Zhou, M. H. A critical review of the application of chelating agents to enable Fenton and Fenton-like reactions at high pH values. J. Hazard. Mater. 2019, 362, 436–450.
DOI Google Scholar
9

Chen, L. W.; Ma, J.; Li, X. C.; Zhang, J.; Fang, J. Y.; Guan, Y. H.; Xie, P. C. Strong enhancement on Fenton oxidation by addition of hydroxylamine to accelerate the ferric and ferrous iron cycles. Environ. Sci. Technol. 2011, 45, 3925–3930.
DOI Google Scholar
10

Yi, Q. Y.; Ji, J. H.; Shen, B.; Dong, C. C.; Liu, J.; Zhang, J. L.; Xing, M. Y. Singlet oxygen triggered by superoxide radicals in a molybdenum cocatalytic Fenton reaction with enhanced REDOX activity in the environment. Environ. Sci. Technol. 2019, 53, 9725–9733.
DOI Google Scholar
11

Xing, M. Y.; Xu, W. J.; Dong, C. C.; Bai, Y. C.; Zeng, J. B.; Zhou, Y.; Zhang, J. L.; Yin, Y. D. Metal sulfides as excellent co-catalysts for H2O2 decomposition in advanced oxidation processes. Chem 2018, 4, 1359–1372.
DOI Google Scholar
12

Dong, C. C.; Ji, J. H.; Shen, B.; Xing, M. Y.; Zhang, J. L. Enhancement of H2O2 decomposition by the co-catalytic effect of WS2 on the Fenton reaction for the synchronous reduction of Cr(VI) and remediation of phenol. Environ. Sci. Technol. 2018, 52, 11297–11308.
DOI Google Scholar
13

Zhou, H. Y.; Peng, J. L.; Li, J. Y.; You, J. J.; Lai, L. D.; Liu, R.; Ao, Z. M.; Yao, G.; Lai, B. Metal-free black-red phosphorus as an efficient heterogeneous reductant to boost Fe3+/Fe2+ cycle for peroxymonosulfate activation. Water Res. 2021, 188, 116529.
DOI Google Scholar
14

Zhou, P.; Ren, W.; Nie, G.; Li, X. J.; Duan, X. G.; Zhang, Y. L.; Wang, S. B. Fast and long-lasting iron(III) reduction by boron toward green and accelerated Fenton chemistry. Angew. Chem. 2020, 132, 16660–16669.
DOI Google Scholar
15

Zhou, P.; Cheng, F.; Nie, G.; Yang, Y. Y.; Hu, K. S.; Duan, X. G.; Zhang, Y. L.; Wang, S. B. Boron carbide boosted Fenton-like oxidation: A novel Fe(III)/Fe(II) circulation. Green Energy Environ. 2020, 5, 414–422.
DOI Google Scholar
16

Wang, Z. Y.; Mi, B. X. Environmental applications of 2D molybdenum disulfide (MoS2) nanosheets. Environ. Sci. Technol. 2017, 51, 8229–8244.
DOI Google Scholar
17

Kumar, R.; Sahoo, S.; Joanni, E.; Singh, R. K.; Yadav, R. M.; Verma, R. K.; Singh, D. P.; Tan, W. K.; del Pino, A. P.; Moshkalev, S. A. et al. A review on synthesis of graphene, h-BN and MoS2 for energy storage applications: Recent progress and perspectives. Nano Res. 2019, 12, 2655–2694.
DOI Google Scholar
18

Gao, X. X.; Yin, J.; Bian, G.; Liu, H. Y.; Wang, C. P.; Pang, X. X.; Zhu, J. High-mobility patternable MoS2 percolating nanofilms. Nano Res. 2021, 14, 2255–2263.
DOI Google Scholar
19

Loh, L.; Zhang, Z. P.; Bosman, M.; Eda, G. Substitutional doping in 2D transition metal dichalcogenides. Nano Res. 2021, 14, 1668–1681.
DOI Google Scholar
20

Wang, Y. N.; Zheng, Y.; Han, C.; Chen, W. Surface charge transfer doping for two-dimensional semiconductor-based electronic and optoelectronic devices. Nano Res. 2021, 14, 1682–1697.
DOI Google Scholar
21

Xie, J. F.; Zhang, J. J.; Li, S.; Grote, F.; Zhang, X. D.; Zhang, H.; Wang, R. X.; Lei, Y.; Pan, B. C.; Xie, Y. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J. Am. Chem. Soc. 2013, 135, 17881–17888.
DOI Google Scholar
22

Yang, B. W.; Chen, Y.; Shi, J. L. Reactive oxygen species (ROS)-based nanomedicine. Chem. Rev. 2019, 119, 4881–4985.
DOI Google Scholar
23

Li, W. Y.; Chen, M.; Zhong, Z. X.; Zhou, M.; Xing, W. H. Hydroxyl radical intensified Cu2O NPs/H2O2 process in ceramic membrane reactor for degradation on DMAc wastewater from polymeric membrane manufacturer. Front. Environ. Sci. Eng. 2020, 14, 102.
DOI Google Scholar
24

Ji, J. H.; Yan, Q. Y.; Yin, P. C.; Mine, S.; Matsuoka, M.; Xing, M. Y. Defects on CoS2−x: Tuning redox reactions for sustainable degradation of organic pollutants. Angew. Chem. 2021, 133, 2939–2944.
DOI Google Scholar
25

Xue, S.; Sun, S. B.; Qing, W. H.; Huang, T. B.; Liu, W.; Liu, C. Q.; Yao, H.; Zhang, W. Experimental and computational assessment of 1, 4-Dioxane degradation in a photo-Fenton reactive ceramic membrane filtration process. Front. Environ. Sci. Eng. 2021, 15, 95.
DOI Google Scholar
26
Wei, Z. L.; Xu, H. L.; Lei, Z. C.; Yi, X. Y.; Feng, C. H.; Dang, Z. A binder-free electrode for efficient H2O2 formation and Fe2+ regeneration and its application to an electro-Fenton process for removing organics in iron-laden acid wastewater. Chin. Chem. Lett., in press, DOI: 10.1016/j.cclet.2021.07.006.
27

Hayyan, M.; Hashim, M. A.; AlNashef, I. M. Superoxide ion: Generation and chemical implications. Chem. Rev. 2016, 116, 3029–3085.
DOI Google Scholar
28

Eisenberg, G. Colorimetric determination of hydrogen peroxide. Ind. Eng. Chem. Anal. Ed. 1943, 15, 327–328.
DOI Google Scholar
29

Stucki, J. W. The quantitative assay of minerals for Fe2+ and Fe3+ using 1,10-phenanthroline: II. A photochemical method. Soil Sci. Soc. Am. J. 1981, 45, 638–641.
DOI Google Scholar
30

Hu, X. K.; Qian, Y. T.; Song, Z. T.; Huang, J. R.; Cao, R.; Xiao, J. Q. Comparative study on MoO3 and HxMoO3 nanobelts: Structure and electric transport. Chem. Mater. 2008, 20, 1527–1533.
DOI Google Scholar
31

Xue, X. Y.; Zhang, J. N.; Saana, I. A.; Sun, J.; Xu, Q.; Mu, S. C. Rational inert-basal-plane activating design of ultrathin 1T′ phase MoS2 with a MoO3 heterostructure for enhancing hydrogen evolution performances. Nanoscale 2018, 10, 16531–16538.
DOI Google Scholar
32

Kibsgaard, J.; Chen, Z. B.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.
DOI Google Scholar
33

Yu, X. Y.; Hu, H.; Wang, Y. W.; Chen, H. Y.; Lou, X. W. Ultrathin MoS2 nanosheets supported on N-doped carbon nanoboxes with enhanced lithium storage and electrocatalytic properties. Angew. Chem. 2015, 127, 7503–7506.
DOI Google Scholar
34

Cai, L.; He, J. F.; Liu, Q. H.; Yao, T.; Chen, L.; Yan, W. S.; Hu, F. C.; Jiang, Y.; Zhao, Y. D.; Hu, T. D. et al. Vacancy-induced ferromagnetism of MoS2 nanosheets. J. Am. Chem. Soc. 2015, 137, 2622–2627.
DOI Google Scholar
35

Liu, Z. P.; Gao, Z. C.; Liu, Y. H.; Xia, M. S.; Wang, R. W.; Li, N. Heterogeneous nanostructure based on 1T-phase MoS2 for enhanced electrocatalytic hydrogen evolution. ACS Appl. Mater. Interfaces 2017, 9, 25291–25297.
DOI Google Scholar
36

Chen, Y.; Zhang, G.; Ji, Q. H.; Liu, H. J.; Qu, J. H. Triggering of low-valence molybdenum in multiphasic MoS2 for effective reactive oxygen species output in catalytic Fenton-like reactions. ACS Appl. Mater. Interfaces 2019, 11, 26781–26788.
DOI Google Scholar
37

Wang, D. Z.; Su, B. Y.; Jiang, Y.; Li, L.; Ng, B. K.; Wu, Z. Z.; Liu, F. Y. Polytype 1T/2H MoS2 heterostructures for efficient photoelectrocatalytic hydrogen evolution. Chem. Eng. J. 2017, 330, 102–108.
DOI Google Scholar
38

Mishra, D.; Farrell, J. Understanding nitrate reactions with zerovalent iron using tafel analysis and electrochemical impedance spectroscopy. Environ. Sci. Technol. 2005, 39, 645–650.
DOI Google Scholar
39

Hu, Y.; Peng, X.; Ai, Z. H.; Jia, F. L.; Zhang, L. Z. Liquid nitrogen activation of zero-valent iron and its enhanced Cr(VI) removal performance. Environ. Sci. Technol. 2019, 53, 8333–8341.
Google Scholar
40

Gallard, H.; De Laat, J. Kinetic modelling of Fe(III)/H2O2 oxidation reactions in dilute aqueous solution using atrazine as a model organic compound. Water Res. 2000, 34, 3107–3116.
DOI Google Scholar
41

Nardi, G.; Manet, I.; Monti, S.; Miranda, M. A.; Lhiaubet-Vallet, V. Scope and limitations of the TEMPO/EPR method for singlet oxygen detection: The misleading role of electron transfer. Free Radic. Biol. Med. 2014, 77, 64–70.
DOI Google Scholar
42

Wang, Y. B.; Cao, D.; Liu, M.; Zhao, X. Insights into heterogeneous catalytic activation of peroxymonosulfate by Pd/g-C3N4: The role of superoxide radical and singlet oxygen. Catal. Commun. 2017, 102, 85–88.
DOI Google Scholar
43

Lee, J.; von Gunten, U.; Kim, J. H. Persulfate-based advanced oxidation: Critical assessment of opportunities and roadblocks. Environ. Sci. Technol. 2020, 54, 3064–3081.
DOI Google Scholar
44

Salgado, P.; Melin, V.; Contreras, D.; Moreno, Y.; Mansilla, H. D. Fenton reaction driven by iron ligands. J. Chil. Chem. Soc. 2013, 58, 2096–2101.
DOI Google Scholar
45

Chen, R. Z.; Pignatello, J. J. Role of Quinone intermediates as electron shuttles in Fenton and photoassisted Fenton oxidations of aromatic compounds. Environ. Sci. Technol. 1997, 31, 2399–2406.
DOI Google Scholar
46

Yamashita, T.; Hayes, P. Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl. Surf. Sci. 2008, 9, 2441–2449.
Google Scholar
47

Boonstra, A. H.; Mutsaers, C. A. H. A. Adsorption of hydrogen peroxide on the surface of titanium dioxide. J. Phys. Chem. 1975, 79, 1940–1943.
DOI Google Scholar
48

Li, X. Z.; Chen, C. C.; Zhao, J. Z. Mechanism of photodecomposition of H2O2 on TiO2 surfaces under visible light irradiation. Langmuir 2001, 17, 4118–4122.
DOI Google Scholar
49

Che, M.; Sojka, Z. Electron transfer processes at the surface of MoOx/SiO2 catalysts. Top. Catal. 2001, 15, 211–217.
DOI Google Scholar
Publication history
Copyright
Acknowledgements

Publication history

Received: 06 July 2021
Revised: 17 August 2021
Accepted: 25 August 2021
Published: 09 September 2021
Issue date: March 2022

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This research was financially supported by the National Natural Science Foundation of China (Nos. 42077293 and 22006088), Natural Science Foundation of Guangdong Province (Nos. 2019A1515011692 and 2019QN01L797), and Shenzhen Municipal Science and Technology Innovation Committee (Nos. JCYJ20190809181413713 and WDZC20200817103015002). Y. X. H. also thanks the financial support from Overseas Cooperation Research Fund of Tsinghua Shenzhen International Graduate School (Nos. HW2020002 and QD2021010N). This work was also supported by the China Postdoctoral Science Foundation (No. 2019M66067).

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