Microchimica Acta

, 186:284 | Cite as

Preparation of an AgI/CuBi2O4 heterojunction on a fluorine-doped tin oxide electrode for cathodic photoelectrochemical assays: application to the detection of L-cysteine

  • Ling Zhang
  • Yu-Liang Shen
  • Gao-Chao Fan
  • Meng XiongEmail author
  • Xiao-Dong YuEmail author
  • Wei-Wei ZhaoEmail author
Original Paper


Photocathodic methods in photoelectrochemical (PEC) analysis are based on the use of functional photocathodes. Heterojunction cathodes consisting of different kinds of semiconductors are being considered as favorite schemes when compared to the single-component ones. A semiconductor heterojunction between CuBi2O4 (CBO) and other semiconductors has not been exploited in PEC assays so far. Herein, CBO nanospheres were initially electrochemically deposited on a fluorine-doped tin oxide (FTO) conductive glass and then coupled to chemically deposited AgI nanoparticles to obtain an electrode of type AgI/CBO/FTO. It was applied as a cathode in the PEC detection of L-cysteine as a model analyte. The sensor can selectively detect L-cysteine, and it is assumed that this is due to the selective interaction between the L-cysteine and both copper and silver via the formation of Cu-S and Ag-S bonds. The photocurrent of the electrode increases linearly with the logarithm of the cysteine concentration in the range from 0.1 and 50 μM, and the detection limit is 0.1 μM.

Graphical abstract

Schematic presentation of the preparation of an AgI/CuBi2O4 (AgI/CBO) heterojunction on a fluorine-doped tin oxide (FTO) electrode and its application to the cathodic photoelectrochemical detection of L-cysteine.


Photoelectrochemical sensing CuBi2O4 AgI Heterojunction Photocathodic sensing 



This work was supported by the National Natural Science Foundation of China (Grant Nos. 21675080, and 21705059) and the Natural Science Foundation of Jiangsu Province (Grant No. BK20170073).

Compliance with ethical standards

The authors declare that they have no competing interests.


  1. 1.
    Wang JW, Xu GQ, Zhang X, Lv J, Zhang XY, Zheng ZX, Wu YC (2015) Electrochemical performance and biosensor application of TiO2 nanotube arrays with mesoporous structures constructed by chemical etching. Dalton Trans 44:7662–7672CrossRefGoogle Scholar
  2. 2.
    He LH, Liu QB, Zhang SJ, Zhang XT, Gong CL, Shu HH, Wang GJ, Liu H, Wen S, Zhang BQ (2018) High sensitivity of TiO2 nanorod array electrode for photoelectrochemical glucose sensor and its photo fuel cell application. Electrochem Commun 94:18–22CrossRefGoogle Scholar
  3. 3.
    He YY, Ge JY, Zhao CZ (2016) Photoelectrochemical response and application of ZnO nanorods photoelectrode to riboflavin. Chem J Chin Univ 37:2144–2149Google Scholar
  4. 4.
    Xi L, Song J, Xu R, Liu DL, Dong B, Xu L, Song HW (2014) Zinc oxide inverse opal electrodes modified by glucose oxidase for electrochemical and photoelectrochemical biosensor. Biosens Bioelectron 59:350–357CrossRefGoogle Scholar
  5. 5.
    Liu Y, Jia SP, Guo LH (2012) Development of microplate-based photoelectrochemical DNA biosensor array for high throughput detection of DNA damage. Sensors Actuators B Chem 161:334–340CrossRefGoogle Scholar
  6. 6.
    Wang J, Xu Q, Xia WW, Shu Y, Jin DQ, Zang Y, Hu XY (2018) High sensitive visible light photoelectrochemical sensor based on in-situ prepared flexible Sn3O4 nanosheets and molecularly imprinted polymers. Sensors Actuators B Chem 271:215–224CrossRefGoogle Scholar
  7. 7.
    Grinyte R, Barroso J, Díez-Buitrago B, Saa L, Möller M, Pavlov V (2017) Photoelectrochemical detection of copper ions by modulating the growth of CdS quantum dots. Anal Chim Acta 986:42–47CrossRefGoogle Scholar
  8. 8.
    Zhao WW, Ma ZY, Yu PP, Dong XY, Xu JJ, Chen HY (2012) Highly sensitive photoelectrochemical immunoassay with enhanced amplification using horseradish peroxidase induced biocatalytic precipitation on a CdS quantum dots multilayer electrode. Anal Chem 84:917–923CrossRefGoogle Scholar
  9. 9.
    Qiu ZL, Shu J, Tang DP (2018) NaYF4:Yb,Er upconversion nanotransducer with in situ fabrication of Ag2S for near-infrared light responsive photoelectrochemical biosensor. Anal Chem 90:12214–−12220CrossRefGoogle Scholar
  10. 10.
    Cui L, Hu J, Wang M, Diao XK, Li CC, Zhang CY (2018) Mimic peroxidase- and Bi2S3 nanorod-based photoelectrochemical biosensor for signal-on detection of polynucleotide kinase. Anal Chem 90:11478–11485CrossRefGoogle Scholar
  11. 11.
    Wang GL, Liu KL, Shu JX, Gu TT, Wu XM, Dong YM, Li ZJ (2015) A novel photoelectrochemical sensor based on photocathode of PbS quantum dots utilizing catalase mimetics of bio-bar-coded platinum nanoparticles/G-quadruplex/hemin for signal amplification. Biosens Bioelectron 69:106–112CrossRefGoogle Scholar
  12. 12.
    Peng B, Tang L, Zeng GM, Fang SY, Ouyang XL, Long BQ, Zhou YY, Deng YC, Liu YN, Wang JJ (2018) Self-powered photoelectrochemical aptasensor based on phosphorus doped porous ultrathin g-C3N4 nanosheets enhanced by surface plasmon resonance effect. Biosens Bioelectron 121:19–26CrossRefGoogle Scholar
  13. 13.
    Wu SY, Huang H, Shang MX, Du CC, Wu Y, Song WB (2017) High visible light sensitive MoS2 ultrathin nanosheets for photoelectrochemical biosensing. Biosens Bioelectron 92:646–653CrossRefGoogle Scholar
  14. 14.
    Qin Q, Bai X, Hua ZL (2017) Electrochemical synthesis of well-dispersed CdTe nanoparticles on reduced graphene oxide and its photoelectrochemical sensing of catechol. J Electrochem Soc 164:H241–H249CrossRefGoogle Scholar
  15. 15.
    Shi XM, Wang CD, Zhu YC, Zhao WW, Yu XD, Xu JJ, Chen HY (2018) 3D semiconducting polymer/graphene networks: toward sensitive photocathodic enzymatic bioanalysis. Anal Chem 90:9687–9690CrossRefGoogle Scholar
  16. 16.
    Yan K, Liu Y, Yang YH, Zhang JD (2015) A cathodic “signal-off” photoelectrochemical aptasensor for ultrasensitive and selective detection of oxytetracycline. Anal Chem 87:12215–12220CrossRefGoogle Scholar
  17. 17.
    Fan GC, Shi XM, Zhang JR, Zhu JJ (2016) Cathode photoelectrochemical immunosensing platform integrating photocathode with photoanode. Anal Chem 88:10352–10356CrossRefGoogle Scholar
  18. 18.
    Jiang XY, Zhang L, Liu YL, Yu XD, Liang YY, Qu P, Zhao WW, Xu JJ, Chen HY (2018) Hierarchical CuInS2-based heterostructure: application for photocathodic bioanalysis of sarcosine. Biosens Bioelectron 107:230–236CrossRefGoogle Scholar
  19. 19.
    Dai WX, Zhang L, Zhao WW, Yu XD, Xu JJ, Chen HY (2017) Hybrid PbS quantum dots/nanoporous NiO films nanostructure: preparation, characterization, and application for novel self-powered cathodic photoelectrochemical biosensor. Anal Chem 89:8070–8078CrossRefGoogle Scholar
  20. 20.
    Li F, Shu JX, Gu TT, Wu XM, Dong YM, Wang GL (2018) Graphene oxide based photocathode for split photoelectrochemical bioanalysis. Electrochem Commun 86:85–89CrossRefGoogle Scholar
  21. 21.
    Wang GL, Liu KL, Dong YM, Wu XM, Li ZJ, Zhang C (2014) A new approach to light up the application of semiconductor nanomaterials for photoelectrochemical biosensors: using self-operating photocathode as a highly selective enzyme sensor. Biosens Bioelectron 62:66–72CrossRefGoogle Scholar
  22. 22.
    Kang Q, Yang LX, Chen YF, Luo SL, Wen LF, Cai QY, Yao SZ (2010) Photoelectrochemical detection of pentachlorophenol with a multiple hybrid CdSexTe1-x/TiO2 nanotube structure-based label-free immunosensor. Anal Chem 82:9749–9754CrossRefGoogle Scholar
  23. 23.
    Ding LH, Ma C, Li L, Zhang LN, Yu JH (2016) A photoelectrochemical sensor for hydrogen sulfide in cancer cells based on the covalently and in situ grafting of CdS nanoparticles onto TiO2 nanotubes. J Electroanal Chem 783:176–181CrossRefGoogle Scholar
  24. 24.
    Kong QK, Cui K, Zhang LN, Wang YH, Sun JL, Ge SG, Zhang Y, Yu JH (2018) "On-off-on" photoelectrochemical/visual lab-on-paper sensing via signal amplification of CdS quantum dots@leaf-shape ZnO and quenching of Au-modified prism-anchored octahedral CeO2 nanoparticles. Anal Chem 90:11297–11304CrossRefGoogle Scholar
  25. 25.
    Zhu YS, Tong XL, Song HZ, Wang YH, Qiao ZQ, Qiu DF, Huang JS, Lu ZW (2018) CsPbBr3 perovskite quantum dots/ZnO inverse opal electrodes: photoelectrochemical sensing for dihydronicotinamide adenine dinucleotide under visible irradiation. Dalton Trans 47:10057–10062CrossRefGoogle Scholar
  26. 26.
    Wu Q, Zhang FX, Li HJ, Li ZH, Kang Q, Shen DZ (2018) A ratiometric photoelectrochemical immunosensor based on g-C3N4@TiO2 NTs amplified by signal antibodies-Co3O4 nanoparticle conjugates. Analyst 143:5030–5037CrossRefGoogle Scholar
  27. 27.
    Ge L, Xu YH, Ding LJ, You FH, Liu Q, Wang K (2019) Perovskite-type BiFeO3/ultrathin graphite-like carbon nitride nanosheets p-n heterojunction: boosted visible-light-driven photoelectrochemical activity for fabricating ampicillin aptasensor. Biosens Bioelectron 124–125:33–39CrossRefGoogle Scholar
  28. 28.
    Yan PC, Jiang DS, Tian YH, Xu L, Qian JC, Li HN, Xia JX, Li HM (2018) A sensitive signal-on photoelectrochemical sensor for tetracycline determination using visible-light-driven flower-like CN/BiOBr composites. Biosens Bioelectron 111:74–81CrossRefGoogle Scholar
  29. 29.
    Wang HY, Yin HS, Huang H, Li KL, Zhou YL, Waterhouse GIN, Lin H, Ai SY (2018) Dual-signal amplified photoelectrochemical biosensor for detection of N6-methyladenosine based on BiVO4-110-TiO2 heterojunction, ag+-mediated cytosine pairs. Biosens Bioelectron 108:89–96CrossRefGoogle Scholar
  30. 30.
    Zhao WW, Liu Z, Shan S, Zhang WW, Wang J, Ma ZY, Xu JJ, Chen HY (2014) Bismuthoxyiodide nanoflakes/titania nanotubes arrayed p-n heterojunction and its application for photoelectrochemical bioanalysis. Sci Rep 4:4426CrossRefGoogle Scholar
  31. 31.
    Cao D, Nasori N, Wang Z, Mi Y, Wen L, Yang Y, Qu S, Wang Z, Lei Y (2016) p-Type CuBi2O4: an easily accessible photocathodic material for high-efficiency water splitting. J Mater Chem A 4:8995–9001CrossRefGoogle Scholar
  32. 32.
    Kang D, Hill JC, Park Y, Choi K (2016) Photoelectrochemical properties and Photostabilities of high surface area CuBi2O4 and Ag-doped CuBi2O4 photocathodes. Chem Mater 28:4331–4340CrossRefGoogle Scholar
  33. 33.
    Hahn NT, Holmberg VC, Korgel BA, Mullins CB (2012) Electrochemical synthesis and characterization of p-CuBi2O4 thin film photocathodes. J Phys Chem C 116:6459–6466CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of BiotechnologyJiangsu University of Science and TechnologyZhenjiangPeople’s Republic of China
  2. 2.Shandong Key Laboratory of Biochemical Analysis, College of Chemistry and Molecular EngineeringQingdao University of Science and TechnologyQingdaoPeople’s Republic of China
  3. 3.State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical EngineeringNanjing UniversityNanjingChina

Personalised recommendations