1. School of Environmental and Safety Engineering, Changzhou University, Changzhou 213164, China 2. Guangxi Key Laboratory of Green Processing of Sugar Resources, College of Biological and Chemical Engineering, Guangxi Science University of and Technology, Liuzhou 545006, China 3. Jiangsu Key Laboratory of Oil-Gas Storage and Transportation Technology, Changzhou University, Changzhou 213164, China 4. Department of Ecosystem Science and Management and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA
A ZnMn2O4 catalyst has been synthesized via a sucrose-aided combustion method and characterized by various analytical techniques. It is composed of numerous nanoparticles (15–110 nm) assembled into a porous structure with a specific surface area (SSA) of 19.1 m2·g–1. Its catalytic activity has been investigated for the degradation of orange II dye using three different systems, i.e., the photocatalysis system with visible light, the chemocatalysis system with bisulfite, and the photo-chemical catalysis system with both visible light and bisulfite. The last system exhibits the maximum degradation efficiency of 90%, much higher than the photocatalysis system (15%) and the chemocatalysis system (67%). The recycling experiments indicate that the ZnMn2O4 catalyst has high stability and reusability and is thus a green and eximious catalyst. Furthermore, the potential degradation mechanisms applicable to the three systems are discussed with relevant theoretical analysis and scavenging experiments for radicals. The active species such as Mn(III), O2•−, h+, eaq–, SO4•− and HO• are proposed to be responsible for the excellent degradation results in the photo-chemical catalysis system with the ZnMn2O4 catalyst.
V K Gupta, I Ali, T A Saleh, A Nayak, S Agarwal. Chemical treatment technologies for waste-water recycling: An overview. RSC Advances, 2012, 2(16): 6380–6388 https://doi.org/10.1039/c2ra20340e
2
J P Li, Y Xu, Y Liu, D Wu, Y H Sun. Synthesis of hydrophilic ZnS nanocrystals and their application in photocatalytic degradation of dye pollutants. China Particuology, 2004, 2(6): 266–269 https://doi.org/10.1016/S1672-2515(07)60072-4
3
M N Chong, B Jin, C W K Chow, C Saint. Recent developments in photocatalytic water treatment technology: A review. Water Research, 2010, 44(10): 2997–3027 https://doi.org/10.1016/j.watres.2010.02.039
4
P R Shukla, S Wang, H M Ang, M O Tadé. Photocatalytic oxidation of phenolic compounds using zinc oxide and sulphate radicals under artificial solar light. Separation and Purification Technology, 2010, 70(3): 338–344 https://doi.org/10.1016/j.seppur.2009.10.018
5
B Ludi, M Niederberger. Zinc oxide nanoparticles: Chemical mechanisms and classical and non-classical crystallization. Dalton Transactions (Cambridge, England), 2013, 42(35): 12554–12568 https://doi.org/10.1039/c3dt50610j
6
S W Liu, C Li, J G Yu, Q J Xiang. Improved visible-light photocatalytic activity of porous carbon self-doped ZnO nanosheet-assembled flowers. CrystEngComm, 2011, 13(7): 2533–2541 https://doi.org/10.1039/c0ce00295j
7
L Duan, B Sun, M Wei, S Luo, F Pan, A Xu, X Li. Catalytic degradation of acid orange 7 by manganese oxide octahedral molecular sieves with peroxymonosulfate under visible light irradiation. Journal of Hazardous Materials, 2015, 285: 356–365 https://doi.org/10.1016/j.jhazmat.2014.12.015
8
R K Hocking, R Brimblecombe, L Y Chang, A Singh, M H Cheah, C Glover, W H Casey, L Spiccia. Water-oxidation catalysis by manganese in a geochemical-like cycle. Nature Chemistry, 2011, 3(6): 461–466 https://doi.org/10.1038/nchem.1049
9
L Zhang, C Yang, Z Xie, X Wang. Cobalt manganese spinel as an effective cocatalyst for photocatalytic water oxidation. Applied Catalysis B: Environmental, 2018, 224: 886–894 https://doi.org/10.1016/j.apcatb.2017.11.023
10
F Cheng, J Shen, B Peng, Y Pan, Z Tao, J Chen. Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts. Nature Chemistry, 2011, 3(1): 79–84 https://doi.org/10.1038/nchem.931
11
Menaka, S L Samal, K V Ramanujachary, S E Lofland, Govind, A K Ganguli. Stabilization of Mn(IV) in nanostructured zinc manganese oxide and their facile transformation from nanospheres to nanorods. Journal of Materials Chemistry, 2011, 21(24): 8566–8573 https://doi.org/10.1039/c1jm10425j
12
C W Cady, G Gardner, Z O Maron, M Retuerto, Y B Go, S Segan, M Greenblatt, G C Dismukes. Tuning the electrocatalytic water oxidation properties of AB2O4 spinel nanocrystals: A (Li, Mg, Zn) and B (Mn, Co) site variants of LiMn2O4. ACS Catalysis, 2015, 5(6): 3403–3410 https://doi.org/10.1021/acscatal.5b00265
13
B Cui, H Lin, Y Z Liu, J B Li, P Sun, X C Zhao, C J Liu. Photophysical and photocatalytic properties of core-ring structured NiCo2O4 nanoplatelets. Journal of Physical Chemistry C, 2009, 113(32): 14083–14087 https://doi.org/10.1021/jp900028t
14
M Khaksar, M Amini, D M Boghaei. Efficient and green oxidative degradation of methylene blue using Mn-doped ZnO nanoparticles (Zn1−xMnxO). Journal of Experimental Nanoscience, 2015, 10(16): 1256–1268 https://doi.org/10.1080/17458080.2014.998300
15
M Qiu, Z Chen, Z Yang, W Li, Y Tian, W Zhang, Y Xu, H Cheng. ZnMn2O4 nanorods: An effective Fenton-like heterogeneous catalyst with t2g3eg1 electronic configuration. Catalysis Science & Technology, 2018, 8(10): 2557–2566 https://doi.org/10.1039/C8CY00436F
16
A V Borhade, D R Tope, G B Dabhade. Removal of erioglaucine dye from aqueous medium using ecofriendly synthesized ZnMnO3 photocatalyst. e-Journal of Surface Science and Nanotechnology, 2017, 15: 74–80
17
C J Li, G R Xu. Zn-Mn-O heterostructures: Study on preparation, magnetic and photocatalytic properties. Materials Science and Engineering B, 2011, 176(7): 552–558 https://doi.org/10.1016/j.mseb.2011.01.011
18
S Yuan, Y Fan, Y Zhang, M Tong, P Liao. Pd-catalytic in situ generation of H2O2 from H2 and O2 produced by water electrolysis for the efficient electro-fenton degradation of rhodamine B. Environmental Science & Technology, 2011, 45(19): 8514–8520 https://doi.org/10.1021/es2022939
19
H Sun, S Z Liu, G Zhou, M Ang, M Tade, S Wang. Reduced graphene oxide for catalytic oxidation of aqueous organic pollutants. ACS Applied Materials & Interfaces, 2012, 4(10): 5466–5471 https://doi.org/10.1021/am301372d
20
Y Guo, X Lou, C Fang, D Xiao, Z Wang, J Liu. Novel photo-sulfite system: Toward simultaneous transformations of inorganic and organic pollutants. Environmental Science & Technology, 2013, 47(19): 11174–11181 https://doi.org/10.1021/es403199p
21
B T Zhang, Y Zhang, Y Teng, M Fan. Sulfate radical and its application in decontamination technologies. Critical Reviews in Environmental Science and Technology, 2015, 45(16): 1756–1800 https://doi.org/10.1080/10643389.2014.970681
22
G P Anipsitakis, D D Dionysiou. Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt. Environmental Science & Technology, 2003, 37(20): 4790–4797 https://doi.org/10.1021/es0263792
23
M G Antoniou, A A de la Cruz, D D Dionysiou. Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e-transfer mechanisms. Applied Catalysis B: Environmental, 2010, 96(3): 290–298 https://doi.org/10.1016/j.apcatb.2010.02.013
24
C Tan, N Gao, Y Deng, Y Zhang, M Sui, J Deng, S Zhou. Degradation of antipyrine by UV, UV/H2O2 and UV/PS. Journal of Hazardous Materials, 2013, 260: 1008–1016 https://doi.org/10.1016/j.jhazmat.2013.06.060
25
C Qi, X Liu, J Ma, C Lin, X Li, H Zhang. Activation of peroxymonosulfate by base: Implications for the degradation of organic pollutants. Chemosphere, 2016, 151: 280–288 https://doi.org/10.1016/j.chemosphere.2016.02.089
26
O S Furman, A L Teel, R J Watts. Mechanism of base activation of persulfate. Environmental Science & Technology, 2010, 44(16): 6423–6428 https://doi.org/10.1021/es1013714
27
Q Yang, H Choi, S R Al-Abed, D D Dionysiou. Iron-cobalt mixed oxide nanocatalysts: Heterogeneous peroxymonosulfate activation, cobalt leaching, and ferromagnetic properties for environmental applications. Applied Catalysis B: Environmental, 2009, 88(3-4): 462–469 https://doi.org/10.1016/j.apcatb.2008.10.013
28
X Chen, J Chen, X Qiao, D Wang, X Cai. Performance of nano-Co3O4/peroxymonosulfate system : Kinetics and mechanism study using acid orange 7 as a model compound. Applied Catalysis B: Environmental, 2008, 80(1-2): 116–121 https://doi.org/10.1016/j.apcatb.2007.11.009
29
K Govindan, M Raja, M Noel, E J James. Degradation of pentachlorophenol by hydroxyl radicals and sulfate radicals using electrochemical activation of peroxomonosulfate, peroxodisulfate and hydrogen peroxide. Journal of Hazardous Materials, 2014, 272(4): 42–51 https://doi.org/10.1016/j.jhazmat.2014.02.036
30
W Jie, Z Hui, J Qiu. Degradation of acid orange 7 in aqueous solution by a novel electro/Fe2+/peroxydisulfate process. Journal of Hazardous Materials, 2012, 215-216(4): 138–145
31
X Liu, X Zhang, K Zhang, C Qi. Sodium persulfate-assisted mechanochemical degradation of tetrabromobisphenol A: Efficacy, products and pathway. Chemosphere, 2016, 150: 551–558 https://doi.org/10.1016/j.chemosphere.2015.08.055
32
X Yan, X Liu, C Qi, D Wang, C Lin. Mechanochemical destruction of a chlorinated polyfluorinated ether sulfonate (F-53B, a PFOS alternative) assisted by sodium persulfate. RSC Advances, 2015, 5(104): 85785–85790 https://doi.org/10.1039/C5RA15337A
33
C Qi, X Liu, Y Li, C Lin, J Ma, X Li, H Zhang. Enhanced degradation of organic contaminants in water by peroxydisulfate coupled with bisulfite. Journal of Hazardous Materials, 2017, 328(Complete): 98–107
34
B Sun, X Guan, J Fang, P G Tratnyek. Activation of manganese oxidants with bisulfite for enhanced oxidation of organic contaminants: The involvement of Mn(III). Environmental Science & Technology, 2015, 49(20): 12414–12421 https://doi.org/10.1021/acs.est.5b03111
35
B Sun, D Li, W Linghu, X Guan. Degradation of ciprofloxacin by manganese(III) intermediate: Insight into the potential application of permanganate/bisulfite process. Chemical Engineering Journal, 2018, 339: 144–152 https://doi.org/10.1016/j.cej.2018.01.131
36
B Sun, H Dong, D He, D Rao, X Guan. Modeling the kinetics of contaminants oxidation and the generation of manganese(III) in the permanganate/bisulfite process. Environmental Science & Technology, 2016, 50(3): 1473–1482 https://doi.org/10.1021/acs.est.5b05207
37
C Zhao, Z Hu, Z Teng, K Liu, D Zhao. Porous ZnMnO3 plates prepared from Zn/Mn-sucrose composite as high-performance lithium-ion battery anodes. Micro & Nano Letters, 2016, 11(9): 494–497 https://doi.org/10.1049/mnl.2016.0239
38
C Cai, Z Zhang, J Liu, N Shan, H Zhang, D D Dionysiou. Visible light-assisted heterogeneous Fenton with ZnFe2O4 for the degradation of orange II in water. Applied Catalysis B: Environmental, 2016, 182: 456–468 https://doi.org/10.1016/j.apcatb.2015.09.056
39
Q Ni, J Ma, C Fan, Y Kong, M Peng, S Komarneni. Spinel-type cobalt-manganese oxide catalyst for degradation of orange II using a novel heterogeneous photo-chemical catalysis system. Ceramics International, 2018, 44(16): 19474–19480 https://doi.org/10.1016/j.ceramint.2018.07.184
40
W D Oh, Z Dong, T T Lim. Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects. Applied Catalysis B: Environmental, 2016, 194: 169–201 https://doi.org/10.1016/j.apcatb.2016.04.003
41
B Xie, X Li, X Huang, Z Xu, W Zhang, B Pan. Enhanced debromination of 4-bromophenol by the UV/sulfite process: Efficiency and mechanism. Journal of Environmental Sciences (China), 2017, 54(4): 231–238 https://doi.org/10.1016/j.jes.2016.02.001
T Xu, R Zhu, G Zhu, J Zhu, X Liang, Y Zhu, H He. Mechanisms for the enhanced photo-Fenton activity of ferrihydrite modified with BiVO4 at neutral pH. Applied Catalysis B: Environmental, 2017, 212: 50–58
T Xu, R Zhu, J Zhu, X Liang, Y Liu, Y Xu, H He. Ag3PO4 immobilized on hydroxy-metal pillared montmorillonite for the visible light driven degradation of acid red 18. Catalysis Science & Technology, 2016, 6(12): 4116–4123 https://doi.org/10.1039/C5CY02129D
46
S Sun, S Pang, J Jiang, J Ma, Z Huang, J Zhang, Y Liu, C Xu, Q Liu, Y Yuan. The combination of ferrate(VI) and sulfite as a novel advanced oxidation process for enhanced degradation of organic contaminants. Chemical Engineering Journal, 2018, 333: 11–19 https://doi.org/10.1016/j.cej.2017.09.082
47
K Ranguelova, A B Rice, A Khajo, M Triquigneaux, S Garantziotis, R S Magliozzo, R P Mason. Formation of reactive sulfite-derived free radicals by the activation of human neutrophils: An ESR study. Free Radical Biology & Medicine, 2012, 52(8): 1264–1271 https://doi.org/10.1016/j.freeradbiomed.2012.01.016
48
J Zou, J Ma, L W Chen, X C Li, Y H Guan, P C Xie, C Pan. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine. Environmental Science & Technology, 2013, 47(20): 11685–11691 https://doi.org/10.1021/es4019145
49
M Liu, Y Du, L Ma, D Jing, L Guo. Manganese doped cadmium sulfide nanocrystal for hydrogen production from water under visible light. International Journal of Hydrogen Energy, 2012, 37(1): 730–736 https://doi.org/10.1016/j.ijhydene.2011.04.111
50
S Paul, P Chetri, A Choudhury. Effect of manganese doping on the optical property and photocatalytic activity of nanocrystalline titania: Experimental and theoretical investigation. Journal of Alloys and Compounds, 2014, 583: 578–586 https://doi.org/10.1016/j.jallcom.2013.08.209
51
S P Mezyk, T J Neubauer, W J Cooper, J R Peller. Free-radical-induced oxidative and reductive degradation of sulfa drugs in water: absolute kinetics and efficiencies of hydroxyl radical and hydrated electron reactions. Journal of Physical Chemistry A, 2007, 111(37): 9019–9024 https://doi.org/10.1021/jp073990k