Electrochemical Sensing of Bisphenol A on Facet-Tailored TiO2 Single Crystals Engineered by Inorganic-Framework Molecular Imprinting Sites

  • Dan-Ni Pei
    Dan-Ni Pei
    CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science & Technology of China, Hefei, 230026, China
    More by Dan-Ni Pei
  • Ai-Yong Zhang*
    Ai-Yong Zhang
    CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science & Technology of China, Hefei, 230026, China
    Department of Municipal Engineering, Hefei University of Technology, Hefei, 230009, China
    *Fax: +86-551-63602449. E-mail: [email protected]
  • Xiao-Qiang Pan
    Xiao-Qiang Pan
    CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science & Technology of China, Hefei, 230026, China
  • Yang Si
    Yang Si
    CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science & Technology of China, Hefei, 230026, China
    More by Yang Si
  • , and 
  • Han-Qing Yu*
    Han-Qing Yu
    CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science & Technology of China, Hefei, 230026, China
    *Fax: +86-551-63601592. E-mail: [email protected]
    More by Han-Qing Yu
Cite this: Anal. Chem. 2018, 90, 5, 3165–3173
Publication Date (Web):February 20, 2018
Copyright © 2018 American Chemical Society
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Noble metals, nanostructured carbon, and their hybrids are widely used for electrochemical detection of persistent organic pollutants. However, despite of the rapid detection process and high accuracy, these materials generally suffer from high costs, metallic impurity, heterogeneity, irreversible adsorption and poor sensitivity. Herein, the high-energy {001}-exposed TiO2 single crystals with specific inorganic-framework molecular recognition ability was prepared as the electrode material to detect bisphenol A (BPA), a typical and widely present organic pollutant in the environment. The oxidation peak current was linearly correlated to the BPA concentration from 10.0 nM to 20.0 μM (R2 = 0.9987), with a low detection limit of 3.0 nM (S/N = 3). Furthermore, it exhibited excellent discriminating ability, high anti-interference capacity, and good long-term stability. Its good performance for BPA detection in real environmental samples, including tap water, lake and river waters, domestic wastewater, and municipal sludge, was also demonstrated. This work extends the applications of TiO2 semiconductor and suggests that this material could be used as a highly active, stable, low-cost, and environmentally benign electrode material for electrochemical sensing.

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem.7b04466.

  • Morphology and structure of P25, calculation for electrochemical surface area, anodic peak potential, initial surface concentration and diffusion coefficient (text), structural parameters of TiO2 (Table S1), initial surface concentration and signal retention efficiency (Table S2), analysis of industrial samples (Table S3), XRD of P25 (Figure S1), SEM of MI-TiO2 (Figure S2), XPS, VB, and BET of TiO2 (Figure S3), electrochemical properties of different electrodes (Figure S4), interfacial diffusion coefficient and initial surface concentration of BPA (Figure S5), it and calculated diffusion coefficients (Figure S6), LSV and relationships between peak current with scanning rate (Figures S7 and S8), DPV of MI-TiO2 (Figures S9–S11), and BPA determination with interferences (Figures S12–S19) (PDF)

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  3. Arif U. Alam, M. Jamal Deen. Bisphenol A Electrochemical Sensor Using Graphene Oxide and β-Cyclodextrin-Functionalized Multi-Walled Carbon Nanotubes. Analytical Chemistry 2020, 92 (7) , 5532-5539. https://doi.org/10.1021/acs.analchem.0c00402
  4. Xiaoyu Li, Caoling Li, Can Wu, Kangbing Wu. Strategy for Highly Sensitive Electrochemical Sensing: In Situ Coupling of a Metal–Organic Framework with Ball-Mill-Exfoliated Graphene. Analytical Chemistry 2019, 91 (9) , 6043-6050. https://doi.org/10.1021/acs.analchem.9b00556
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  6. Mohamed A. Shenashen, Mohammed Y. Emran, Ayman El Sabagh, Mahmoud M. Selim, Ahmed Elmarakbi, Sherif A. El-Safty. Progress in sensory devices of pesticides, pathogens, coronavirus, and chemical additives and hazards in food assessment: Food safety concerns. Progress in Materials Science 2022, 124 , 100866. https://doi.org/10.1016/j.pmatsci.2021.100866
  7. Krishnan Venkatesh, Balamurugan Muthukutty, Shen-Ming Chen, Periyakaruppan Karuppasamy, Ahmed S. Haidyrah, Chelladurai Karuppiah, Chun-Chen Yang, Sayee Kannan Ramaraj. Spinel CoMn2O4 nano-/micro-spheres embedded RGO nanosheets modified disposable electrode for the highly sensitive electrochemical detection of metol. Journal of Industrial and Engineering Chemistry 2021, 6 https://doi.org/10.1016/j.jiec.2021.11.005
  8. Zhi Li, Jiayue Hu, Zaizhu Lou, Lixi Zeng, Mingshan Zhu. Molecularly imprinted photoelectrochemical sensor for detecting tetrabromobisphenol A in indoor dust and water. Microchimica Acta 2021, 188 (10) https://doi.org/10.1007/s00604-021-04980-1
  9. Zhou Xu, Yanqiu Chen, Maolong Chen, Wei Chen, Yunhui Cheng. Assembly of USPIO/MOF nanoparticles with high proton relaxation rates for ultrasensitive magnetic resonance sensing. Journal of Materials Chemistry C 2021, 9 (35) , 11915-11923. https://doi.org/10.1039/D1TC01524A
  10. Sujuan Hu, Yongqi Wei, Jiao Wang, Yingjian Yu. A photo-renewable ZIF-8 photo-electrochemical sensor for the sensitive detection of sulfamethoxazole antibiotic. Analytica Chimica Acta 2021, 1178 , 338793. https://doi.org/10.1016/j.aca.2021.338793
  11. Lan Wang, Huan Zhang, Hang Shi, Baodan Jin, Xiaoyun Qin, Geng Wang, Kucong Li, Tingting Zhang, Hongzhong Zhang. In-site synthesis of an inorganic-framework molecular imprinted TiO 2 /CdS heterostructure for the photoelectrochemical sensing of bisphenol A. Analytical Methods 2021, 13 (25) , 2857-2864. https://doi.org/10.1039/D1AY00620G
  12. Qiaowei Chen, Chen Yuan, Chunyang Zhai. Label-free photoelectrochemical sensor based on 2D/2D ZnIn2S4/g-C3N4 heterojunction for the efficient and sensitive detection of bisphenol A. Chinese Chemical Letters 2021, 10 https://doi.org/10.1016/j.cclet.2021.07.047
  13. Luyun Jiang, Ibon Santiago, John Foord. A comparative study of fouling-free nanodiamond and nanocarbon electrochemical sensors for sensitive bisphenol A detection. Carbon 2021, 174 , 390-395. https://doi.org/10.1016/j.carbon.2020.11.073
  14. Ana-Mihaela Gavrila, Ionut-Cristian Radu, Hermine Stroescu, Anamaria Zaharia, Elena-Bianca Stoica, Ana-Lorena Ciurlica, Tanţa-Verona Iordache, Andrei Sârbu. Role of Functional Monomers upon the Properties of Bisphenol A Molecularly Imprinted Silica Films. Applied Sciences 2021, 11 (7) , 2956. https://doi.org/10.3390/app11072956
  15. Zhou Xu, Rong Wang, Yanqiu Chen, Maolong Chen, Jian Zhang, Yunhui Cheng, Jianguo Xu, Wei Chen. Three-dimensional assembly and disassembly of Fe3O4-decorated porous carbon nanocomposite with enhanced transversal relaxation for magnetic resonance sensing of bisphenol A. Microchimica Acta 2021, 188 (3) https://doi.org/10.1007/s00604-021-04718-z
  16. Zhi Li, Jiayue Hu, Yongguang Xiao, Qingbing Zha, Lixi Zeng, Mingshan Zhu. Surfactant assisted Cr-metal organic framework for the detection of bisphenol A in dust from E-waste recycling area. Analytica Chimica Acta 2021, 1146 , 174-183. https://doi.org/10.1016/j.aca.2020.11.021
  17. S. Irem Kaya, Ahmet Cetinkaya, Sibel A. Ozkan. Latest Advances in Determination of Bisphenols with Nanomaterials, Molecularly Imprinted Polymers and Aptamer Based Electrochemical Sensors. Critical Reviews in Analytical Chemistry 2021, , 1-21. https://doi.org/10.1080/10408347.2020.1864719
  18. Giuseppe Mele, Roberta Del Sole, Xiangfei Lü. Applications of TiO2 in sensor devices. 2021,,, 527-581. https://doi.org/10.1016/B978-0-12-819960-2.00004-3
  19. Dhurkasini Ananthakrishnan, Harikrishnan Venkatesvaran, Aarthi Kannan, Sakthivel Gandhi. Simplistic one-pot synthesis of an inorganic–organic cubic caged material: a new interface for detecting toxic bisphenol-A electrochemically. New Journal of Chemistry 2020, 44 (46) , 20192-20202. https://doi.org/10.1039/D0NJ05142J
  20. Yinhui Yi, Depeng Zhang, Panlei An, Gangbing Zhu. Nitrogen Coordinated Copper Co-Doped Multi-Walled Carbon Nanotubes for High-Efficiency Electrochemical Sensing of Bisphenol A. Journal of The Electrochemical Society 2020, 167 (14) , 146515. https://doi.org/10.1149/1945-7111/abc7e3
  21. Guoneng Cai, Zhenzhong Yu, Dianping Tang. Actuating photoelectrochemical sensing sensitivity coupling core-core-shell [email protected]@TiO2 with molecularly imprinted polypyrrole. Talanta 2020, 219 , 121341. https://doi.org/10.1016/j.talanta.2020.121341
  22. Jianying Pei, Yu Yang, Yuning Jiang, Yifei Huang, Xiaoyu Guo, Ye Ying, Ying Wen, Haifeng Yang, Yiping Wu. Surface Plasmon Resonance Boosting Photoelectrochemical System for Ultrasensitive Detection of Bisphenol A. Journal of The Electrochemical Society 2020, 167 (12) , 127508. https://doi.org/10.1149/1945-7111/abadbe
  23. Zhaoyi Liu, Tao Fan, Yong Zhang, Xiang Ren, Yaoguang Wang, Hongmin Ma, Qin Wei. Electrochemical assay of ampicillin using Fe3N-Co2N nanoarray coated with molecularly imprinted polymer. Microchimica Acta 2020, 187 (8) https://doi.org/10.1007/s00604-020-04432-2
  24. Chengxin Xu, Lingbo Liu, Can Wu, Kangbing Wu. Unique 3D heterostructures assembled by quasi-2D Ni-MOF and CNTs for ultrasensitive electrochemical sensing of bisphenol A. Sensors and Actuators B: Chemical 2020, 310 , 127885. https://doi.org/10.1016/j.snb.2020.127885
  25. Yang Deng, Zhen Zhang, Peiyao Du, Xingming Ning, Yue Wang, Dongxu Zhang, Jia Liu, Shouting Zhang, Xiaoquan Lu. Embedding Ultrasmall Au Clusters into the Pores of a Covalent Organic Framework for Enhanced Photostability and Photocatalytic Performance. Angewandte Chemie 2020, 132 (15) , 6138-6145. https://doi.org/10.1002/ange.201916154
  26. Yang Deng, Zhen Zhang, Peiyao Du, Xingming Ning, Yue Wang, Dongxu Zhang, Jia Liu, Shouting Zhang, Xiaoquan Lu. Embedding Ultrasmall Au Clusters into the Pores of a Covalent Organic Framework for Enhanced Photostability and Photocatalytic Performance. Angewandte Chemie International Edition 2020, 59 (15) , 6082-6089. https://doi.org/10.1002/anie.201916154
  27. Yueqiang Lin, Zhuangjun Fan. Compositing strategies to enhance the performance of chemiresistive CO2 gas sensors. Materials Science in Semiconductor Processing 2020, 107 , 104820. https://doi.org/10.1016/j.mssp.2019.104820
  28. Zhengpeng Yang, Tongtong Qin, Yutao Niu, Yongyi Zhang, Chunjing Zhang, Ping Li, Meng Zhu, Yuanheng Jia, Qingwen Li. Flexible visible-light-driven photoelectrochemical biosensor based on molecularly imprinted nanoparticle intercalation-modulated graphene fiber for ultrasensitive urea detection. Carbon 2020, 157 , 457-465. https://doi.org/10.1016/j.carbon.2019.10.061
  29. Bhargav R. Patel, Meissam Noroozifar, Kagan Kerman. Review—Nanocomposite-Based Sensors for Voltammetric Detection of Hazardous Phenolic Pollutants in Water. Journal of The Electrochemical Society 2020, 167 (3) , 037568. https://doi.org/10.1149/1945-7111/ab71fa
  30. Li-Ping Mei, Pei Song, Yuan-Cheng Zhu, Yi-Fan Ruan, Xiao-Mei Shi, Wei-Wei Zhao, Jing-Juan Xu, Hong-Yuan Chen. Recent Advances in Electrochemical Sensor and Biosensors for Environmental Contaminants. 2020,,, 1-31. https://doi.org/10.1007/978-3-030-45116-5_1
  31. Hongwu Wang, Yanqing Liu, Gengxin Hu, Yinjian Ye, Lingling Pan, Peijie Zhu, Su Yao. Ultrasensitive electrochemical sensor for determination of trace carbadox with ordered mesoporous carbon/GCE. Journal of Electroanalytical Chemistry 2020, 857 , 113736. https://doi.org/10.1016/j.jelechem.2019.113736
  32. Vinoj Vasu, Murali Rangarajan. Semi-empirical simulations of interactions between edge-functionalized graphene oxide and bisphenol A. Materials Today: Proceedings 2020, 23 , 85-90. https://doi.org/10.1016/j.matpr.2019.07.405
  33. Mingzhu Yu, Lina Wu, Jiaona Miao, Wei Wei, Anran Liu, Songqin Liu. Titanium dioxide and polypyrrole molecularly imprinted polymer nanocomposites based electrochemical sensor for highly selective detection of p-nonylphenol. Analytica Chimica Acta 2019, 1080 , 84-94. https://doi.org/10.1016/j.aca.2019.06.053
  34. Yong Zhang, Xiaoyuan Chen. Nanotechnology and nanomaterial-based no-wash electrochemical biosensors: from design to application. Nanoscale 2019, 11 (41) , 19105-19118. https://doi.org/10.1039/C9NR05696C
  35. Rong Chai, Xianwen Kan. Au-polythionine nanocomposites: a novel mediator for bisphenol A dual-signal assay based on imprinted electrochemical sensor. Analytical and Bioanalytical Chemistry 2019, 411 (17) , 3839-3847. https://doi.org/10.1007/s00216-019-01858-3
  36. Hadi Beitollahi, Hadi Mahmoudi Moghaddam, Somayeh Tajik. Voltammetric Determination of Bisphenol A in Water and Juice Using a Lanthanum (III)-Doped Cobalt (II,III) Nanocube Modified Carbon Screen-Printed Electrode. Analytical Letters 2019, 52 (9) , 1432-1444. https://doi.org/10.1080/00032719.2018.1545132
  37. Yang Si, Ai-Yong Zhang, Chang Liu, Dan-Ni Pei, Han-Qing Yu. Photo-assisted electrochemical detection of bisphenol A in water samples by renewable {001}-exposed TiO2 single crystals. Water Research 2019, 157 , 30-39. https://doi.org/10.1016/j.watres.2019.03.088
  38. Jun Ye, Xing Li, Qiyan Li, Teng Qiu, Longhai Guo, Lifan He, Xiaoyu Li. The building of molecular imprinted sites on the Stöber spheres of resorcinol-formaldehyde resin: In situ organic vs. inorganic imprinting method. Materials Chemistry and Physics 2019, 230 , 239-248. https://doi.org/10.1016/j.matchemphys.2019.03.057
  39. Zhaoyi Liu, Yong Zhang, Jinhui Feng, Qingzhi Han, Qin Wei. Ni(OH)2 nanoarrays based molecularly imprinted polymer electrochemical sensor for sensitive detection of sulfapyridine. Sensors and Actuators B: Chemical 2019, 287 , 551-556. https://doi.org/10.1016/j.snb.2019.02.079
  40. Ramzan Ullah, Xiangzhao Wang. Raman scattering excited with 532 nm laser in bisphenol “AF” and its connection with bisphenol “A” and “S”. Spectroscopy Letters 2019, 52 (3-4) , 183-193. https://doi.org/10.1080/00387010.2019.1597737
  41. Arockiajawahar Anancia Grace, Karutha Pandian Divya, Venkataraman Dharuman, Jong Hoon Hahn. Single step sol-gel synthesized Mn2O3-TiO2 decorated graphene for the rapid and selective ultra sensitive electrochemical sensing of dopamine. Electrochimica Acta 2019, 302 , 291-300. https://doi.org/10.1016/j.electacta.2019.02.053
  42. Haydar Ali, Soumita Mukhopadhyay, Nikhil R. Jana. Selective electrochemical detection of bisphenol A using a molecularly imprinted polymer nanocomposite. New Journal of Chemistry 2019, 43 (3) , 1536-1543. https://doi.org/10.1039/C8NJ05883K
  43. Somayeh Tajik, Hadi Mahmoudi-Moghaddam, Hadi Beitollahi. Screen-Printed Electrode Modified with La 3+ -Doped Co 3 O 4  Nanocubes for Electrochemical Determination of Hydroxylamine. Journal of The Electrochemical Society 2019, 166 (6) , B402-B406. https://doi.org/10.1149/2.0491906jes
  44. Muthumariappan Akilarasan, Sakthivel Kogularasu, Shen-Ming Chen, Tse-Wei Chen, Shih-Hao Lin. One-step synthesis of reduced graphene oxide sheathed zinc oxide nanoclusters for the trace level detection of bisphenol A in tissue papers. Ecotoxicology and Environmental Safety 2018, 161 , 699-705. https://doi.org/10.1016/j.ecoenv.2018.06.045