TiO2 Nanotube Array Photoelectrocatalyst and Ni–Sb–SnO2 Electrocatalyst Bifacial Electrodes: A New Type of Bifunctional Hybrid Platform for Water Treatment

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School of Energy Engineering, Kyungpook National University, Daegu 702-701, Korea
School of Environmental Science and Engineering, POSTECH, Pohang 790-784, Korea
*Telephone: +82-53-950-8973. Fax: +82-53-950-8979. E-mail: [email protected]
Cite this: ACS Appl. Mater. Interfaces 2015, 7, 3, 1907–1914
Publication Date (Web):January 5, 2015
Copyright © 2015 American Chemical Society
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Bifunctional hybrid electrodes capable of generating various reactive oxygen species (ROS) over a wide range of potentials were developed by coupling electrocatalysts and photoelectrocatalysts. To achieve this, Ni-doped Sb-SnO2 (NSS) was deposited on one side of a titanium (Ti) foil while the other side was anodized to grow a TiO2 nanotube array (TNA) for electrochemical ozone generation and photoelectrochemical hydroxyl radical generation, respectively. Surface characterization indicated that NSS and TNA were formed and spatially separated yet electrically connected through the Ti substrate. While each catalyst possessed unique electrochemical properties, the coupling of both catalysts resulted in mixed electrochemical properties that drove electrocatalysis at high potentials and photoelectrocatalysis at low potentials. The performance of the NSS/TNA electrode for phenol decomposition was ∼3 times greater than that of single-layer catalysts and ∼1.5 times greater than the combined catalytic performances of the individual NSS and TNA catalysts. This synergistic effect was attributed partly to the simultaneous generation of hydroxyl radicals and ozone, followed by the production of other ROS. A mechanism for the generation of ROS was discussed.

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  4. Hyunwoong Park. Solar remediation of wastewater and saline water with concurrent production of value-added chemicals. Journal of Environmental Chemical Engineering 2021, 110 , 106919.
  5. Churat Weeraphan, Pongsakorn Thawornpan, Supinya Thanapongpichat, Kanitta Srinoun, Aung Win Tun, Chantragan Srisomsap, Jisnuson Svasti, Hansuk Buncherd. Application of the Magnetic Fraction of Fly Ash as a Low-Cost Heterogeneous Fenton Catalyst for Degrading Ethidium Bromide. Analytical Letters 2021, 21 , 1-15.
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  11. Jingyun Zhao, Zexu Chi, Heng Dong, Changfu Sun, Han Yu, Hongbing Yu. Degradation of desphenyl chloridazon in a novel synergetic electrocatalytic system with Ni–Sb–SnO2/Ti anode and PEDOT/PSS-CNTs modified air diffusion cathode. Journal of Cleaner Production 2021, 300 , 126961.
  12. Lei Zhao, Xinqi Zhang, Zhimeng Liu, Cheng Deng, Huimin Xu, Yin Wang, Mengfu Zhu. Carbon nanotube-based electrocatalytic filtration membrane for continuous degradation of flow-through Bisphenol A. Separation and Purification Technology 2021, 265 , 118503.
  13. Wonjung Choi, Jun Hyeok Choi, Hyunwoong Park. Electrocatalytic activity of metal-doped SnO2 for the decomposition of aqueous contaminants: Ta-SnO vs. Sb-SnO. Chemical Engineering Journal 2021, 409 , 128175.
  14. Bin Zhao, Hongbin Yu, Yanpeng Liu, Ying Lu, Wei Fan, Weichao Qin, Mingxin Huo. Enhanced photoelectrocatalytic degradation of acetaminophen using a bifacial electrode of praseodymium-polyethylene glycol-PbO2//Ti//TiO2-nanotubes. Chemical Engineering Journal 2021, 410 , 128337.
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  22. Abdullah Al-Hamdi, Mika Sillanpää. Photocatalytic activities of antimony, iodide, and rare earth metals on SnO2 for the photodegradation of phenol under UV, solar, and visible light irradiations. 2020,,, 129-288.
  23. Hye Won Jeong, Kyu Jun Park, Yiseul Park, Dong Suk Han, Hyunwoong Park. Exploring the photoelectrocatalytic behavior of free-standing TiO2 nanotube arrays on transparent conductive oxide electrodes: Irradiation direction vs. alignment direction. Catalysis Today 2019, 335 , 319-325.
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  26. So Young Yang, Chad D. Vecitis, Hyunwoong Park. Electrocatalytic water treatment using carbon nanotube filters modified with metal oxides. Environmental Science and Pollution Research 2019, 26 (2) , 1036-1043.
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  40. Yong Chen, Yong Tu, Yaohui Zhang, Jiaang Lu, Binbin Fang. Fabrication and enhanced electrocatalytic activity of TiO 2 nanotubes based three-dimensionally macroporous SnO 2 with mesoporous walls. Chemical Engineering Journal 2017, 311 , 100-110.
  41. Chong Fu, Mingji Li, Hongji Li, Cuiping Li, Xiao guo Wu, Baohe Yang. Fabrication of Au nanoparticle/TiO2 hybrid films for photoelectrocatalytic degradation of methyl orange. Journal of Alloys and Compounds 2017, 692 , 727-733.
  42. Zhongxue Yang, Huying Wang, Weijie Song, Wei Wei, Qingping Mu, Bo Kong, Peiqiang Li, Hongzong Yin. One dimensional SnO2 NRs/Fe2O3 NTs with dual synergistic effects for photoelectrocatalytic reduction CO2 into methanol. Journal of Colloid and Interface Science 2017, 486 , 232-240.
  43. Xinyang Li, Yue Wu, Wei Zhu, Fangqing Xue, Yi Qian, Chengwen Wang. Enhanced electrochemical oxidation of synthetic dyeing wastewater using SnO 2 -Sb-doped TiO 2 -coated granular activated carbon electrodes with high hydroxyl radical yields. Electrochimica Acta 2016, 220 , 276-284.
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  46. J.L. Qiao, Q.Y. Wang, J.X. Ye, Y.K. Xiao. Enhancing photoelectrochemical performance of TiO2 nanotube arrays by CdS and Bi2S3 co-sensitization. Journal of Photochemistry and Photobiology A: Chemistry 2016, 319-320 , 34-39.
  47. Qingyao Wang, Xiaotong Wang, Miao Zhang, Guihua Li, Shanmin Gao, Mingyang Li, Yiqing Zhang. Influence of Ag–Au microstructure on the photoelectrocatalytic performance of TiO 2 nanotube array photocatalysts. Journal of Colloid and Interface Science 2016, 463 , 308-316.
  48. Qingyao Wang, Chao Chen, Wei Liu, Shanmin Gao, Xiuchun Yang. Recent progress in all-solid-state quantum dot-sensitized TiO2 nanotube array solar cells. Journal of Nanoparticle Research 2016, 18 (1)
  49. Linlin Zhang, Zipeng Xing, Hang Zhang, Zhenzi Li, Xiaoyan Wu, Xiaodong Zhang, Yan Zhang, Wei Zhou. High thermostable ordered mesoporous SiO2–TiO2 coated circulating-bed biofilm reactor for unpredictable photocatalytic and biocatalytic performance. Applied Catalysis B: Environmental 2016, 180 , 521-529.
  50. Hyunwoong Park, Hyoung-il Kim, Gun-hee Moon, Wonyong Choi. Photoinduced charge transfer processes in solar photocatalysis based on modified TiO 2. Energy & Environmental Science 2016, 9 (2) , 411-433.
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  52. Sung-Ho Hwang, Young Kwang Kim, Song Hyun Yoon, Sang Kyoo Lim, Hyunwoong Park. ZnO rods rooted on manifold carbon nanofiber paper as a scalable photocatalyst platform: the effects of ZnO morphology. RSC Advances 2016, 6 (88) , 85521-85528.
  53. Tigang Duan, Ye Chen, Qing Wen, Ying Duan, Lijuan Qi. Component-Controlled Synthesis of Gradient Electrode for Efficient Electrocatalytic Dye Decolorization. Journal of The Electrochemical Society 2016, 163 (7) , H499-H507.