Advanced Electrochemical Oxidation of 1,4-Dioxane via Dark Catalysis by Novel Titanium Dioxide (TiO2) Pellets

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Department of Chemistry, Department of Soil and Crop Sciences and §Department of Civil and Environmental Engineering, Colorado State University, Fort Collins, Colorado 80523, United States
*Phone: 1-970-491-8880; fax: 1-970-491-8224; e-mail: [email protected]
Cite this: Environ. Sci. Technol. 2016, 50, 16, 8817–8826
Publication Date (Web):July 15, 2016
Copyright © 2016 American Chemical Society
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1,4-dioxane is an emerging groundwater contaminant with significant regulatory implications. Because it is resistant to traditional groundwater treatments, remediation of 1,4-dioxane is often limited to costly ex situ UV-based advanced oxidation. By varying applied voltage, electrical conductivity, seepage velocity, and influent contaminant concentration in flow-through reactors, we show that electrochemical oxidation is a viable technology for in situ and ex situ treatment of 1,4-dioxane under a wide range of environmental conditions. Using novel titanium dioxide (TiO2) pellets, we demonstrate for the first time that this prominent catalyst can be activated in the dark even when electrically insulated from the electrodes. TiO2-catalyzed reactors achieved efficiencies of greater than 97% degradation of 1,4-dioxane, up to 4.6 times higher than noncatalyzed electrolytic reactors. However, the greatest catalytic enhancement (70% degradation versus no degradation without catalysis) was observed in low-ionic-strength water, where conventional electrochemical approaches notoriously fail. The TiO2 pellet’s dark-catalytic oxidation activity was confirmed on the pharmaceutical lamotrigine and the industrial solvent chlorobenzene, signifying that electrocatalytic treatment has tremendous potential as a transformative remediation technology for persistent organic pollutants in groundwater and other aqueous environments.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.6b02183.

  • Details on analytical methods and experimental design, TiO2 pellet fabrication, catalyst characterization, FTER results, and additional mechanistic experiments. Figures showing key steps in the process of making catalytic TiO2 pellets to be used as interelectrode catalysts, photo of a FTER with inter-electrode TiO2 pellets between four working electrodes, experimental set up showing the noncatalyzed control FTER with inter-electrode glass beads and the TiO2-catalyzed FTER, circular Ti–IrO2-Ta2O5 mesh electrode, a top-view of the pulverized TiO2 after shaking pellets in the glass vial, schematic of FTER, chemical structures of persistent organic pollutants, SEM images of TiO2 pellet surface, data characterizing TiO2 pellets sintered for 4 hours, relative distribution of initial TOC, schematic showing the top view of a concentric cylindrical electrode batch reactor with Nafion membrane to separate inner anodic chamber from the outer cathodic chamber, and degradation efficiencies of 1,4-dioxane in 5.0 cm I.D. flow-through electrochemical reactors. Tables showing results and test criteria used to evaluate mechanical stability of finished TiO2 pellets, summary of results from FTER experiments, flow-parameter calculations using hydraulic mass continuity and Darcy equations, triplicate TOC data, and chromatographic retention times and ESI-TOF-MS data for dioxane intermediates. (PDF)

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  9. Shan Xue, Shaobin Sun, Weihua Qing, Taobo Huang, Wen Liu, Changqing Liu, Hong Yao, Wen Zhang. Experimental and computational assessment of 1,4-Dioxane degradation in a photo-Fenton reactive ceramic membrane filtration process. Frontiers of Environmental Science & Engineering 2021, 15 (5)
  10. Zhang Chengli, Ma Ronghua, We Qi, Yang Mingrui, Cao Rui, Zong Xiaonan. Photocatalytic degradation of organic pollutants in wastewater by heteropolyacids: a review. Journal of Coordination Chemistry 2021, 74 (11) , 1751-1764.
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  14. Vu Khac Hoang Bui, Vinh Van Tran, Ju-Young Moon, Duckshin Park, Young-Chul Lee. Titanium Dioxide Microscale and Macroscale Structures: A Mini-Review. Nanomaterials 2020, 10 (6) , 1190.
  15. Tingting Yu, WenWei Wu, Lifen Liu, Changfei Gao, Tao Yang. Novel ternary p-ZnIn2S4/rGO/n-g-C3N4 Z-scheme nanocatalyst with enhanced antibiotic degradation in a dark self-biased fuel cell. Ceramics International 2020, 46 (7) , 9567-9574.
  16. Ursula Karges, Diana Ott, Sabrina De Boer, Wilhelm Püttmann. 1,4-Dioxane contamination of German drinking water obtained by managed aquifer recharge systems: Distribution and main influencing factors. Science of The Total Environment 2020, 711 , 134783.
  17. Farbod Sharif, Edward P.L. Roberts. Anodic electrochemical regeneration of a graphene/titanium dioxide composite adsorbent loaded with an organic dye. Chemosphere 2020, 241 , 125020.
  18. Farbod Sharif, Edward P. L. Roberts. Electrochemical Oxidation of an Organic Dye Adsorbed on Tin Oxide and Antimony Doped Tin Oxide Graphene Composites. Catalysts 2020, 10 (2) , 263.
  19. Ciara Byrne, Stephen Rhatigan, Daphne Hermosilla, Noemí Merayo, Ángeles Blanco, Marie Clara Michel, Steven Hinder, Michael Nolan, Suresh C Pillai. Modification of TiO 2 with hBN: high temperature anatase phase stabilisation and photocatalytic degradation of 1,4-dioxane. Journal of Physics: Materials 2020, 3 (1) , 015009.
  20. Ramesh Aryal, Chunjie Xia, Jia Liu. 1,4‐Dioxane‐contaminated groundwater remediation in the anode chamber of a microbial fuel cell. Water Environment Research 2019, 91 (11) , 1537-1545.
  21. Krystal J. Godri Pollitt, Jae-Hong Kim, Jordan Peccia, Menachem Elimelech, Yawei Zhang, Georgia Charkoftaki, Brenna Hodges, Ines Zucker, Huang Huang, Nicole C. Deziel, Kara Murphy, Momoko Ishii, Caroline H. Johnson, Andrea Boissevain, Elaine O'Keefe, Paul T. Anastas, David Orlicky, David C. Thompson, Vasilis Vasiliou. 1,4-Dioxane as an emerging water contaminant: State of the science and evaluation of research needs. Science of The Total Environment 2019, 690 , 853-866.
  22. Kimberly N. Heck, Yehong Wang, Gang Wu, Feng Wang, Ah-Lim Tsai, David T. Adamson, Michael S. Wong. Effectiveness of metal oxide catalysts for the degradation of 1,4-dioxane. RSC Advances 2019, 9 (46) , 27042-27049.
  23. Amie C. McElroy, Michael R. Hyman, Detlef R.U. Knappe. 1,4-Dioxane in drinking water: emerging for 40 years and still unregulated. Current Opinion in Environmental Science & Health 2019, 7 , 117-125.
  24. Jens Blotevogel, Charles Pijls, Bert Scheffer, Jean-Paul de Waele, Amy Lee, Reggy van Poecke, Nicolaas van Belzen, Wim Staal. Pilot-Scale Electrochemical Treatment of a 1,4-Dioxane Source Zone. Groundwater Monitoring & Remediation 2019, 39 (1) , 36-42.
  25. Linduo Zhao, Xia Lu, Alexandra Polasko, Nicholas W. Johnson, Yu Miao, Ziming Yang, Shaily Mahendra, Baohua Gu. Co-contaminant effects on 1,4-dioxane biodegradation in packed soil column flow-through systems. Environmental Pollution 2018, 243 , 573-581.
  26. Wanyi Fu, Wen Zhang. Microwave-enhanced membrane filtration for water treatment. Journal of Membrane Science 2018, 568 , 97-104.
  27. Naresh Mameda, Hyeona Park, Kwang-Ho Choo. Electrochemical filtration process for simultaneous removal of refractory organic and particulate contaminants from wastewater effluents. Water Research 2018, 144 , 699-708.
  28. Hyeona Park, Naresh Mameda, Kwang-Ho Choo. Catalytic metal oxide nanopowder composite Ti mesh for electrochemical oxidation of 1,4-dioxane and dyes. Chemical Engineering Journal 2018, 345 , 233-241.
  29. Lei Huang, Minfang Zheng, Dongqi Yu, Muhammad Yaseen, Lianjie Duan, Wentao Jiang, Liyi Shi. In-situ fabrication and catalytic performance of [email protected] core-shell nanowires on copper meshes/foams. Materials & Design 2018, 147 , 182-190.
  30. Shu Zhang, Phillip B. Gedalanga, Shaily Mahendra. Advances in bioremediation of 1,4-dioxane-contaminated waters. Journal of Environmental Management 2017, 204 , 765-774.
  31. Huanqi He, Zhi Zhou. Electro-Fenton process for water and wastewater treatment. Critical Reviews in Environmental Science and Technology 2017, 47 (21) , 2100-2131.
  32. Qiang Zeng, Hailiang Dong, Xi Wang, Tian Yu, Weihua Cui. Degradation of 1, 4-dioxane by hydroxyl radicals produced from clay minerals. Journal of Hazardous Materials 2017, 331 , 88-98.
  33. Xing Ding, Shengyao Wang, Wanqiu Shen, Yi Mu, Li Wang, Hao Chen, Lizhi Zhang. [email protected] 2 O 3 promoted electrochemical mineralization of atrazine via a triazinon ring opening mechanism. Water Research 2017, 112 , 9-18.