Citation: Sun Yanhui, Qi Youxiao, Shen You, Jing Cuijie, Chen Xiaoxiao, Wang Xinxing. Preparation of Electrochemical Sensor Based on RGO-Au-ZIF-8 Composite and Its Application in Simultaneous Detection of Lead Ions and Copper Ions[J]. Acta Chimica Sinica, ;2020, 78(2): 147-154. doi: 10.6023/A19090338 shu

Preparation of Electrochemical Sensor Based on RGO-Au-ZIF-8 Composite and Its Application in Simultaneous Detection of Lead Ions and Copper Ions

a.
College of Environmental and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042
b.
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042

Corresponding author: Sun Yanhui, sunyh@qust.edu.cn Wang Xinxing, wangxx@qust.edu.cn
Received Date: 12 September 2019
Available Online: 10 February 2020
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21804076), the Natural Science Foundation of Shandong Province (No. ZR2017BB040), the Applied Basic Research Program of Qingdao (No. 17-1-1-65-jch) and the Open Fund of Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, Ministry of Education, Qingdao University of Science and Technology (No. SATM201708)the Natural Science Foundation of Shandong Province ZR2017BB040the Open Fund of Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, Ministry of Education, Qingdao University of Science and Technology SATM201708the Applied Basic Research Program of Qingdao 17-1-1-65-jchthe National Natural Science Foundation of China 21804076

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Metal organic frameworks (MOFs) have unique advantages in adsorption and preconcentration of heavy metal ions due to their structure and composition characteristics, which make them show great potential in optical sensing of heavy metal ions. However, their applications in the field of electrochemical sensing is greatly limited because of their poor conductivity. In this work, a functionalized MOF composite, thermally reduced graphene oxide-Au nanoparticles-zeolitic imidazolate skeleton material (RGO-Au-ZIF-8), was fabricated. It exhibits much improved electrochemical properties compared with the pristine MOF. A novel electrochemical sensing platform was constructed based on it, and simultaneous detection of lead ions (Pb²⁺) and copper ions (Cu²⁺) in aqueous solution was realized. Specifically, the Au-ZIF-8 was prepared by adding polyvinylpyrrolidone (PVP)-stabilized Au nanoparticles (AuNPs) to the reaction solution of ZIF-8. The modification of AuNPs effectively improved the conductivity of the material. After compounding with RGO, the RGO-Au-ZIF-8 composite was prepared. The RGO was used as scaffold for the Au-ZIF-8 in the composite to increase the effective surface area of electrode and improve conductivity. The morphology and structure of the prepared materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-visible absorption spectroscopy (UV-Vis). The electrochemical properties of the modified electrodes were characterized by various electrochemical techniques. The experimental parameters, such as pH value of working solution, accumulation potential, accumulation time and composition ratio of Au-ZIF-8 to RGO were optimized. Under the optimized conditions, simultaneous and sensitive detection of Pb²⁺ and Cu²⁺ on the prepared electrochemical sensor was realized with the detection limits of 2.6×10^-9 and 7.8×10^-9 mol·L^-1 for Pb²⁺ and Cu²⁺, respectively (S/N=3). The interference test showed that the electrochemical sensor has good selectivity for the detection of Pb²⁺ and Cu²⁺, and further electrochemical studies revealed that the designed sensor has excellent reproducibility and good stability. The result of recovery test indicated that the prepared electrochemical sensor has great potential in Pb²⁺ and Cu²⁺ detection in real water samples. This work provides a new platform for simultaneous, rapid and sensitive detection of heavy metal ions, and greatly expands the electrochemical applications of MOF materials.
1. [1]
  Awual, M. R.; Hasan, M. M.; Shahat, A. Sens. Actuators, B 2014, 203, 854. doi: 10.1016/j.snb.2014.07.063
2. [2]
  Rodriguez Martin, J. A.; De Arana, C.; Ramos-Miras, J. J.; Gil, C.; Boluda, R. Environ. Pollut. 2015, 196, 156. doi: 10.1016/j.envpol.2014.10.014
3. [3]
  Saha, D.; Barakat, S.; Bramer, S. V.; Nelson, K. A.; Hensley, D. K.; Chen, J. H. ACS Appl. Mater. Interfaces 2016, 8, 34132. doi: 10.1021/acsami.6b12190
4. [4]
  Mo, J.; Zhou, L.; Li, X.; Li, Q.; Wang, L.; Wang, Z. Microchem. J. 2017, 130, 353. doi: 10.1016/j.microc.2016.10.008
5. [5]
  Choi, H. W.; Lee, K. H.; Hur, N. H.; Lim, H. B. Anal. Chim. Acta 2014, 847, 10. doi: 10.1016/j.aca.2014.08.041
6. [6]
  Zeinu, K. M.; Hou, H. J.; Liu, B. C.; Yuan, X. Q.; Long, H.; Zhu, X. L.; Hu, J. P.; Yang, J. K.; Liang, S.; Wu, X. J. J. Mater. Chem. A 2016, 4, 13967. doi: 10.1039/C6TA04881A
7. [7]
  Zhang, Z. H.; Ji, H. F.; Song, Y. P.; Zhang, S.; Wang, M. H.; Jia, C. C.; Tian, J. Y.; He, L. H.; Zhang, X. J.; Liu, C. S. Biosens. Bioelectron. 2017, 94, 358. doi: 10.1016/j.bios.2017.03.014
8. [8]
  Cui, L.; Wu, J.; Li, J.; Ju, H. X. Anal. Chem. 2015, 87, 10635. doi: 10.1021/acs.analchem.5b03287
9. [9]
  Li, L. B.; Liu, D.; Shi, A. P.; You, T. Y. Sens. Actuators, B 2018, 255, 1762. doi: 10.1016/j.snb.2017.08.190
10. [10]
  Zhou, S. F.; Wang, J. J.; Gan, L.; Han, X. J.; Fan, H. L.; Mei, L. Y.; Huang, J.; Liu, Y. Q. J. Alloy. Compd. 2017, 721, 492. doi: 10.1016/j.jallcom.2017.05.321
11. [11]
  Lv, H. Y.; Teng, Z. Y.; Wang, S. C.; Feng, K.; Wang, X. L.; Wang, C. Y.; Wang, G. X. Sens. Actuators, B 2018, 256, 98. doi: 10.1016/j.snb.2017.10.053
12. [12]
  Zhu, G. F.; Chen, L. T.; Cheng, G. H.; Zhao, J.; Yang, C.; Zhang, Y. Z.; Wang, X.; Fan, J. Acta Chim. Sinica 2019, 77, 434.
13. [13]
  Ma, Y. L.; Liu, R. X.; Meng, S. Y.; Niu, L. T.; Yang, Z. W.; Lei, Z. Q. Acta Chim. Sinica 2019, 77, 153.
14. [14]
  Zhang, H.; Li, G. L.; Zhang, K. G.; Liao, C. Y. Acta Chim. Sinica 2017, 75, 841.
15. [15]
  Li, Y.; Zou, B.; Xiao, A. S.; Zhang, H. X. Chin. J. Chem. 2017, 35, 1501. doi: 10.1002/cjoc.201700151
16. [16]
  Sun, D. R.; Li, Z. H. Chin. J. Chem. 2017, 35, 135. doi: 10.1002/cjoc.201600647
17. [17]
  Lu, M. X.; Deng, Y. J.; Luo, Y.; Lv, J. P.; Li, T. B.; Xu, J.; Chen, S. W.; Wang, J. Y. Anal. Chem. 2019, 91, 888. doi: 10.1021/acs.analchem.8b03764
18. [18]
  Guo, H. L.; Zhu, G. S.; Hewitt, L. J.; Qiu, S. L. J. Am. Chem. Soc. 2009, 131, 1646. doi: 10.1021/ja8074874
19. [19]
  Banerjee, R.; Britt, H. F. D.; Knobler, C.; O'Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2009, 131, 3875. doi: 10.1021/ja809459e
20. [20]
  Li, Y. S.; Liang, F. Y.; Bux, H.; Feldhoff, A.; Yang, W. S.; Caro, J. Angew. Chem., Int. Ed. 2010, 49, 548. doi: 10.1002/anie.200905645
21. [21]
  Chizallet, C.; Lazare, S.; Bazer-Bachi, D.; Bonnier, F.; Lecocq, V.; Soyer, E.; Quoineaud, A. A.; Bats, N. J. Am. Chem. Soc. 2010, 132, 2365.
22. [22]
  Guo, X. L.; Chen, X.; Su, D. S.; Liang, C. H. Acta Chim. Sinica 2018, 76, 22. doi: 10.3866/PKU.WHXB201706302
23. [23]
  Qiu, S. L.; Zhu, G. S. Coord. Chem. Rev. 2009, 253, 2891. doi: 10.1016/j.ccr.2009.07.020
24. [24]
  Yang, T.; Cui, Y. N.; Chen, H. Y.; Li, W. H. Acta Chim. Sinica 2017, 75, 339.
25. [25]
  Gao, S. S.; Xu, C. Y.; Yalikun, N.; Mamat, X.; Li, Y. T.; Wagberg, T.; Hu, X.; Liu, J.; Luo, J.; Hu, G. Z. J. Electrochem. Soc. 2017, 164, H967. doi: 10.1149/2.1611713jes
26. [26]
  Xiao, L. L.; Xu, H. B.; Zhou, S. H.; Song, T.; Wang, H. H.; Li, S. Z.; Gan, W.; Yuan, Q. H. Electrochim. Acta 2014, 143, 143. doi: 10.1016/j.electacta.2014.08.021
27. [27]
  Personick, M. L.; Langille, M. R.; Zhang, J.; Mirkin, C. A. Nano Lett. 2011, 11, 3394. doi: 10.1021/nl201796s
28. [28]
  Zhang, Z. X.; Luan, W. X.; Zhang, C. Y.; Liu, Y. J. Acta Chim. Sinica 2017, 75, 403. doi: 10.7503/cjcu20160717
29. [29]
  Zhu, X. L.; Liu, B. C.; Hou, H. J.; Huang, Z. Y.; Zeinu, K. M.; Huang, L.; Yuan, X. Q.; Guo, D. B.; Hu, J. P.; Yang, J. K. Electrochim. Acta 2017, 248, 46. doi: 10.1016/j.electacta.2017.07.084
30. [30]
  Wang, Y.; Wang, L.; Huang, W.; Zhang, T.; Hu, X. Y.; Perman, J. A.; Ma, S. Q. J. J. Mater. Chem. A 2017, 5, 8385. doi: 10.1039/C7TA01066D
31. [31]
  Wei, Y.; Gao, C.; Meng, F. L.; Li, H. H.; Wang, L.; Liu, J. H.; Huang, X. J. J. Phys. Chem. C 2011, 116, 1034.
32. [32]
  Guo, Z.; Li, D. D.; Luo, X. K.; Li, Y. H.; Zhao, Q. N.; Li, M. M.; Zhao, Y. T.; Sun, T. S.; Ma, C. J. Colloid Interface Sci. 2017, 490, 11. doi: 10.1016/j.jcis.2016.11.006
33. [33]
  Yu, L. Y.; Zhang, Q.; Yang, B. R.; Xu, Q.; Xu, Q.; Hu, X. Y. Sens. Actuators, B 2018, 259, 540. doi: 10.1016/j.snb.2017.12.103
34. [34]
  Frens, G. Nat. Phys. Sci. 1973, 241, 20. doi: 10.1038/physci241020a0
35. [35]
  Lu, G.; Li, S.; Guo, Z.; Farha, O. K.; Hauser, B. G.; Qi, X.; Wang, Y.; Wang, X.; Han, S.; Liu, X.; Duchene, J. S.; Zhang, H.; Zhang, Q.; Chen, X.; Ma, J.; Loo, S. C.; Wei, W. D.; Yang, Y.; Hupp, J. T.; Huo, F. Nat. Chem. 2012, 4, 310. doi: 10.1038/nchem.1272
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