Interlayer-confined two-dimensional manganese oxide-carbon nanotube catalytic ozonation membrane for efficient water purification

Abstract

Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity. However, its extensive industrial application has been restricted by the low ozone utilization and limited mass transfer of the short-lived radical species. Interlayer space-confined catalysis has been theoretically proven to be a viable strategy for achieving high catalytic efficiency. Here, a two-dimensional MnO₂-incorporated ceramic membrane with tunable interspacing, which was obtained via the intercalation of a carbon nanotube, was designed as a catalytic ozonation membrane reactor for degrading methylene blue. Benefiting from the abundant catalytic active sites on the surface of two-dimensional MnO₂ as well as the ultralow mass transfer resistance of fluids due to the nanolayer confinement, an excellent mineralization effect, i.e., 1.2 mg O_3(aq) mg^–1 TOC removal (a total organic carbon removal rate of 71.5%), was achieved within a hydraulic retention time of 0.045 s of pollutant degradation. Further, the effects of hydraulic retention time and interlayer spacing on methylene blue removal were investigated. Moreover, the mechanism of the catalytic ozonation employing catalytic ozonation membrane was proposed based on the contribution of the Mn(III/IV) redox pair to electron transfer to generate the reactive oxygen species. This innovative two-dimensional confinement catalytic ozonation membrane could act as a nanoreactor and separator to efficiently oxidize organic pollutants and enhance the control of membrane fouling during water purification.

Graphical abstract

Keywords

catalytic membrane reactor / catalytic ozonation / nanoconfinement / two-dimensional manganese oxide

References

[1] Nguyen T A, Juang R. Treatment of waters and wastewaters containing sulfur dyes: a review. Chemical Engineering Journal, 2013, 219: 109–117

[2] Katheresan V, Kansedo J, Lau S Y. Efficiency of various recent wastewater dye removal methods: a review. Journal of Environmental Chemical Engineering, 2018, 6(4): 4676–4697

[3] Spagni A, Casu S, Grilli S. Decolourisation of textile wastewater in a submerged anaerobic membrane bioreactor. Bioresource Technology, 2012, 117: 180–185

[4] García-Montaño J, Torrades F, García-Hortal J A, Domènech X, Peral J. Combining photo-Fenton process with aerobic sequencing batch reactor for commercial hetero-bireactive dye removal. Applied Catalysis B: Environmental, 2006, 67(1–2): 86–92

[5] Paździor K, Bilińska L, Ledakowicz S. A review of the existing and emerging technologies in the combination of AOPs and biological processes in industrial textile wastewater treatment. Chemical Engineering Journal, 2019, 376: 120597

[6] Nawrocki J, Kasprzyk-Hordern B. The efficiency and mechanisms of catalytic ozonation. Applied Catalysis B: Environmental, 2010, 99(1–2): 27–42

[7] Harman B I, Koseoglu H, Yigit N O, Beyhan M, Kitis M. The use of iron oxide-coated ceramic membranes in removing natural organic matter and phenol from waters. Desalination, 2010, 261(1–2): 27–33

[8] Byun S, Davies S H, Alpatova A L, Corneal L M, Baumann M J, Tarabara V V, Masten S J. Mn oxide coated catalytic membranes for a hybrid ozonation-membrane filtration: comparison of Ti, Fe and Mn oxide coated membranes for water quality. Water Research, 2011, 45(1): 163–170

[9] Lee W J, Bao Y, Guan C, Hu X, Lim T. Ce/TiO_x-functionalized catalytic ceramic membrane for hybrid catalytic ozonation-membrane filtration process: fabrication, characterization and performance evaluation. Chemical Engineering Journal, 2021, 410: 128307

[10] Wang J, Wu Z, Li T, Ye J, Shen L, She Z, Liu F. Catalytic PVDF membrane for continuous reduction and separation of p-nitrophenol and methylene blue in emulsified oil solution. Chemical Engineering Journal, 2018, 334: 579–586

[11] Ma J, Graham N J D. Degradation of atrazine by manganese-catalysed ozonation: influence of humic substances. Water research (Oxford), 1999, 33(3): 785–793

[12] Sun Q, Wang Y, Li L, Bing J, Wang Y, Yan H. Mechanism for enhanced degradation of clofibric acid in aqueous by catalytic ozonation over MnO/SBA-15. Journal of Hazardous Materials, 2015, 286: 276–284

[13] Zhao Y, Chang C, Teng F, Zhao Y, Chen G, Shi R, Waterhouse G I N, Huang W, Zhang T. Defect-engineered ultrathin δ-MnO₂ nanosheet arrays as bifunctional electrodes for efficient overall water splitting. Advanced Energy Materials, 2017, 7(18): 1700005

[14] Rong S, Zhang P, Wang J, Liu F, Yang Y, Yang G, Liu S. Ultrathin manganese dioxide nanosheets for formaldehyde removal and regeneration performance. Chemical Engineering Journal, 2016, 306: 1172–1179

[15] Liu J, Wei Y, Li P, Zhang P, Su W, Sun Y, Zou R, Zhao Y. Experimental and theoretical investigation of mesoporous MnO₂ nanosheets with oxygen vacancies for high-efficiency catalytic DeNO_x. ACS Catalysis, 2018, 8(5): 3865–3874

[16] Zhu L, Chen M, Dong Y, Tang C Y, Huang A, Li L. A low-cost mullite-titania composite ceramic hollow fiber microfiltration membrane for highly efficient separation of oil-in-water emulsion. Water Research, 2016, 90: 277–285

[17] Liu Z, Xu K, Sun H, Yin S. One-step synthesis of single-layer MnO₂ nanosheets with multi-role sodium dodecyl sulfate for high-performance pseudocapacitors. Small, 2015, 11(18): 2182–2191

[18] Tan X, Wan Y, Huang Y, He C, Zhang Z, He Z, Hu L, Zeng J, Shu D. Three-dimensional MnO₂ porous hollow microspheres for enhanced activity as ozonation catalysts in degradation of bisphenol A. Journal of Hazardous Materials, 2017, 321: 162–172

[19] Cui L, Huang H, Ding P, Zhu S, Jing W, Gu X. Cogeneration of H₂O₂ and •OH via a novel Fe₃O₄/MWCNTs composite cathode in a dual-compartment electro-Fenton membrane reactor. Separation and Purification Technology, 2020, 237: 116380

[20] Lee W J, Bao Y, Hu X, Lim T. Hybrid catalytic ozonation-membrane filtration process with CeO_x and MnO_x impregnated catalytic ceramic membranes for micropollutants degradation. Chemical Engineering Journal, 2019, 378: 121670

[21] Chiou C, Mariñas B J, Adams J Q. Modified indigo method for gaseous and aqueous ozone analyses. Ozone Science and Engineering, 1995, 17(3): 329–344

[22] Kai K, Yoshida Y, Kageyama H, Saito G, Ishigaki T, Furukawa Y, Kawamata J. Room-temperature synthesis of manganese oxide monosheets. Journal of the American Chemical Society, 2008, 130(47): 15938–15943

[23] Wang X, Li Y. Synthesis and formation mechanism of manganese dioxide nanowires/nanorods. Chemistry (Weinheim an der Bergstrasse, Germany), 2003, 9(1): 300–306

[24] Devaraj S, Munichandraiah N. Effect of crystallographic structure of MnO₂ on its electrochemical capacitance properties. Journal of Physical Chemistry C, 2008, 112(11): 4406–4417

[25] Rong S, Zhang P, Liu F, Yang Y. Engineering crystal facet of α-MnO₂ nanowire for highly efficient catalytic oxidation of carcinogenic airborne formaldehyde. ACS Catalysis, 2018, 8(4): 3435–3446

[26] Sinha A K, Pradhan M, Pal T. Morphological evolution of two-dimensional MnO₂ nanosheets and their shape transformation to one-dimensional ultralong MnO₂ nanowires for robust catalytic activity. Journal of Physical Chemistry C, 2013, 117(45): 23976–23986

[27] Yang D S, Wang M K. Syntheses and characterization of well-crystallized birnessite. Chemistry of Materials, 2001, 13(8): 2589–2594

[28] Xu J, Li Y, Qian M, Pan J, Ding J, Guan B. Amino-functionalized synthesis of MnO₂-NH₂-GO for catalytic ozonation of cephalexin. Applied Catalysis B: Environmental, 2019, 256: 117797

[29] Nawaz F, Cao H, Xie Y, Xiao J, Chen Y, Ghazi Z A. Selection of active phase of MnO₂ for catalytic ozonation of 4-nitrophenol. Chemosphere, 2017, 168: 1457–1466

[30] Zhao H, Dong Y, Jiang P, Wang G, Zhang J, Li K, Feng C. An α-MnO₂ nanotube used as a novel catalyst in ozonation: performance and the mechanism. New Journal of Chemistry, 2014, 38(4): 1175–1743

[31] Li G, Lu Y, Lu C, Zhu M, Zhai C, Du Y, Yang P. Efficient catalytic ozonation of bisphenol-A over reduced graphene oxide modified sea urchin-like α-MnO₂ architectures. Journal of Hazardous Materials, 2015, 294: 201–208

[32] Qi F, Chen Z, Xu B, Shen J, Ma J, Joll C, Heitz A. Influence of surface texture and acid-base properties on ozone decomposition catalyzed by aluminum (hydroxyl) oxides. Applied Catalysis B: Environmental, 2008, 84(3–4): 684–690

[33] Sui M, Liu J, Sheng L. Mesoporous material supported manganese oxides (MnO_x/MCM-41) catalytic ozonation of nitrobenzene in water. Applied Catalysis B: Environmental, 2011, 106: 197–203

[34] Turan-Ertas T, Gurol M D. Oxidation of diethylene glycol with ozone and modified Fenton processes. Chemosphere, 2002, 47(3): 293–301

[35] Zhang S, Quan X, Zheng J, Wang D. Probing the interphase “HO·zone” originated by carbon nanotube during catalytic ozonation. Water Research, 2017, 122: 86–95

[36] Wang Y, Chen L, Chen C, Xi J, Cao H, Duan X, Xie Y, Song W, Wang S. Occurrence of both hydroxyl radical and surface oxidation pathways in N-doped layered nanocarbons for aqueous catalytic ozonation. Applied Catalysis B: Environmental, 2019, 254: 283–291

[37] Zhang J, Wu Y, Qin C, Liu L, Lan Y. Rapid degradation of aniline in aqueous solution by ozone in the presence of zero-valent zinc. Chemosphere, 2015, 141: 258–264

[38] Huang K, Liu G, Lou Y, Dong Z, Shen J, Jin W. A graphene oxide membrane with highly selective molecular separation of aqueous organic solution. Angewandte Chemie International Edition, 2014, 53(27): 6929–6932

[39] Rana M, Sai Avvaru V, Boaretto N, de la Peña O’Shea V A, Marcilla R, Etacheri V, Vilatela J J. High rate hybrid MnO₂@CNT fabric anodes for Li-ion batteries: properties and a lithium storage mechanism study by in situ synchrotron X-ray scattering. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(46): 26596–26606

[40] Lu K, Hu Z, Xiang Z, Ma J, Song B, Zhang J, Ma H. Cation intercalation in manganese oxide nanosheets: effects on lithium and sodium storage. Angewandte Chemie International Edition, 2016, 55(35): 10448–10452

[41] Byun S, Cho S H, Yoon J, Geissen S U, Vogelpohl A, Kim S M. Influence of mass transfer on the ozonation of wastewater from the glass fiber industry. Water Science and Technology, 2004, 49(4): 31–36

[42] Saroj D P, Kumar A, Bose P, Tare V, Dhopavkar Y. Mineralization of some natural refractory organic compounds by biodegradation and ozonation. Water Research, 2005, 39(9): 1921–1933

[43] Rosal R, Rodríguez A, Perdigón-Melón J A, Mezcua M, Hernando M D, Letón P, García-Calvo E, Agüera A, Fernández-Alba A R. Removal of pharmaceuticals and kinetics of mineralization by O₃/H₂O₂ in a biotreated municipal wastewater. Water Research, 2008, 42(14): 3719–3728

[44] Chen Y, Zhang G, Liu H, Qu J. Confining free radicals in close vicinity to contaminants enables ultrafast Fenton-like processes in the interspacing of MoS₂ membranes. Angewandte Chemie International Edition, 2019, 58(24): 8134–8138

[45] Biswas S, Pal A. Visible light assisted Fenton type degradation of methylene blue by admicelle anchored alumina supported rod shaped manganese oxide. Journal of Water Process Engineering, 2020, 36: 101272

[46] Xu A, Li X, Xiong H, Yin G. Efficient degradation of organic pollutants in aqueous solution with bicarbonate-activated hydrogen peroxide. Chemosphere, 2011, 82(8): 1190–1195

[47] Luo X, Liang H, Qu F, Ding A, Cheng X, Tang C Y, Li G. Free-standing hierarchical α-MnO₂@CuO membrane for catalytic filtration degradation of organic pollutants. Chemosphere, 2018, 200: 237–247

Acknowledgments

This study was financially supported by the National Natural Science Foundation of China (Grant Nos. 21838005 and 21676139) and the Key Scientific Research and Development Projects of Jiangsu Province (Grant No. BE201800901). The authors would like to thank Shiyanjia Laboratory for the language editing service.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-021-2110-6 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2021 Higher Education Press