Copper-Supported Crosslinked Chitosan–Glutaraldehyde/Zinc Oxide: Interfacial Structure, Cyclic Voltammetric Behavior, and Reproducibility

Anceu Murniati; Restu Muchammad  Ibrahim; Intan Mulya  Ewangga; Rolan  Rusli

doi:10.15408/jkv.v12i1.46454

Authors

Anceu Murniati Study Program of Master of Chemistry, Faculty of Sciences and Informatics, Universitas Jenderal Achmad Yani https://orcid.org/0000-0001-6667-3134
Restu Muchammad Ibrahim Study Program of Master of Chemistry, Faculty of Sciences and Informatics, Universitas Jenderal Achmad Yani
Intan Mulya Ewangga Study Program of Master of Chemistry, Faculty of Sciences and Informatics, Universitas Jenderal Achmad Yani
Rolan Rusli Pharmaceutical Chemistry Division, Faculty of Pharmacy, Mulawarman University

DOI:

https://doi.org/10.15408/jkv.v12i1.46454

Keywords:

Cyclic voltammetry, diffusion-controlled electron transfer, interfacial structure, reproducibility, zinc oxide–crosslinked chitosan coating

Abstract

Chitosan-based nanocomposite coatings are promising low-cost electrochemical materials, but the relationship between interfacial structure and voltammetric performance remains insufficiently understood. This study investigated the cyclic voltammetric behavior, reproducibility, and cycling stability of a copper-supported crosslinked chitosan–glutaraldehyde/zinc oxide coating. Structural and electrochemical characterization was performed using Fourier transform infrared spectroscopy, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and cyclic voltammetry in 0.1 M phosphate-buffered saline and 0.01 M K₃[Fe(CN)₆]/0.10 M KCl. The coating showed Schiff-base crosslinking, Zn-related interactions, compact morphology, good attachment to copper, and distributed Zn-containing domains without obvious large-scale agglomeration. Electrochemically, the coating exhibited quasi-reversible behavior in both media. Ferricyanide produced sharper redox features, current ratios closer to unity, and stronger anodic linearity with the square root of scan rate than phosphate-buffered saline. The apparent diffusion coefficient estimated from the ferricyanide anodic response was on the order of 10⁻⁵–10⁻⁶ cm² s⁻¹. Reproducibility across ten independently prepared electrodes was acceptable, with lower variability in ferricyanide than in phosphate-buffered saline, and the voltammetric profile was retained over 15 cycles. These results demonstrate a stable and reasonably reproducible electrochemical interface with potential for future sensing applications.

Downloads

Download data is not yet available.

References

1. Azizi SN, Ghasemi S, Amiripour F. Nickel/P Nanozeolite Modified Electrode: A New Sensor for the Detection of Formaldehyde. Sens Actuators B Chem. 2016;227:1-10. doi:10.1016/j.snb.2015.11.142

2. Zhou ZL, Kang TF, Zhang Y, Cheng SY. Electrochemical Sensor For Formaldehyde based on Pt-Pd Nanoparticles and A Nafion-Modified Glassy Carbon Electrode. Microchimica Acta. 2009;164(1-2):133-138. doi:10.1007/s00604-008-0046-x

3. Momeni S, Sedaghati F. CuO/Cu2O nanoparticles: A simple and Green Synthesis, Characterization and Their Electrocatalytic Performance Toward Formaldehyde Oxidation. Microchemical Journal. 2018;143:64-71. doi:10.1016/j.microc.2018.07.035

4. Rahman MM. Efficient Formaldehyde Sensor Development Based On Cu-Codoped Zno Nanomaterial By an Electrochemical Approach. Sens Actuators B Chem. 2020;305:127541. doi:10.1016/j.snb.2019.127541

5. Hosseini SR, Raoof JB, Ghasemi S, Gholami Z. Pd-Cu/poly(o-anisidine) Nanocomposite as an Efficient Catalyst for Formaldehyde Oxidation. Mater Res Bull. 2016;80:107-119. doi:10.1016/j.materresbull.2016.03.040

6. Hajilari F, Farhadi K, Eskandari H, Allahnouri F. Application of Cu/porous Silicon Nanocomposite Screen Printed Sensor for The Determination of Formaldehyde. Electrochim Acta. 2020;355:1-8. doi:10.1016/j.electacta.2020.136751

7. Zhang H, Yun S, Song L, Zhang Y, Zhao Y. The Preparation and Characterization of Chitin and Chitosan under Large-Scale Submerged Fermentation Level using Shrimp By-Products As Substrate. Int J Biol Macromol. 2017;96:334-339. doi:10.1016/j.ijbiomac.2016.12.017

8. Vedula SS, Yadav GD. Chitosan-based Membranes Preparation and Applications: Challenges and opportunities. Journal of the Indian Chemical Society. 2021;98(2):1-14. doi:10.1016/j.jics.2021.100017

9. Saputra HA, Andreas. Chitosan and its biomedical applications: A review. Next Materials. 2025;9. doi:10.1016/j.nxmate.2025.101270

10. Karim MM, Lasker T, Sahin AZ, Hossain S, Saputra HA. Low-Cost Production of Chitosan Biopolymer from Seafood Waste: Extraction and Physiochemical Characterization. Vol 12.; 2023.

11. Liu CY, Chou YC, Tsai JH, Huang TM, Chen JZ, Yeh YC. Tyrosinase/Chitosan/Reduced Graphene Oxide Modified Screen-Printed Carbon Electrode for Sensitive and Interference-Free Detection of Dopamine. Applied Sciences (Switzerland). 2019;9(4):1-9. doi:10.3390/app9040622

12. Sun C, Zou Y, Wang D, Geng Z, Xu W, Liu F, Cao J. Construction of chitosan-Zn-Based Electrochemical Biosensing Platform for Rapid and Accurate Assay of Actin. Sensors (Switzerland). 2018;18(6):1-13. doi:10.3390/s18061865

13. Eljali A, Nainggolan I, Hashim S, Nasution TI, Wahab NZA. Fabrication of Chitosan-Polyethylene Oxide Polymeric Thin Film using Electrochemical Deposition for Detection of Volatile Organic Compounds. Key Eng Mater. 2017;744 744 KE:359-363. doi:10.4028/www.scientific.net/KEM.744.359

14. Sanjari AJ, Asghari M. A Review on Chitosan Utilization in Membrane Synthesis. ChemBioEng Reviews. 2016;3(3):134-158. doi:10.1002/cben.201500020

15. Application of Chitosan/Fe3O4 Nanocomposite as Biosensor. Letters in Applied NanoBioScience. 2021;10(3):2438-2445. doi:10.33263/lianbs103.24382445

16. Liu P, Yin L, Qi X. Application of Glassy Carbon Electrode Modified with Chitosan and ZnO Nanoparticles as Enzymatic Glucose Biosensor. Int J Electrochem Sci. 2020;15:5821-5832. doi:10.20964/2020.06.67

17. Figiela M, Wysokowski M, Galinski M, Jesionowski T, Stepniak I. Synthesis and Characterization of Novel Copper Oxide-Chitosan Nanocomposites for Non-Enzymatic Glucose Sensing. Sens Actuators B Chem. 2018;272:296-307. doi:10.1016/j.snb.2018.05.173

18. Liu L, Pan Z. Properties of Hydrophilic Chitosan/Polysulfone Nanofibrous Filtration Membrane. J Eng Fiber Fabr. 2014;9(1):76-86. doi:10.1177/155892501400900109

19. Beppu MM, Vieira RS, Aimoli CG, Santana CC. Crosslinking of Chitosan Membranes using Glutaraldehyde: Effect on Ion Permeability and Water Absorption. J Memb Sci. 2007;301(1-2):126-130. doi:10.1016/j.memsci.2007.06.015

20. Galan J, Trilleras J, Zapata PA, Arana VA, Grande-Tovar CD. Optimization of Chitosan Glutaraldehyde-Crosslinked Beads for Reactive Blue 4 Anionic Dye Removal Using a Surface Response Methodology. 2021;11(2):1-20. doi:10.3390/life11020085

21. Bui TH, Lee W, Jeon SB, Kim KW, Lee Y. Enhanced Gold(III) Adsorption using Glutaraldehyde-Crosslinked Chitosan Beads: Effect of Crosslinking Degree on Adsorption Selectivity, Capacity, and Mechanism. Sep Purif Technol. 2020;248:1-12. doi:10.1016/j.seppur.2020.116989

22. Wang ZL. Zinc Oxide Nanostructures: Growth, Properties and Applications. Journal of Physics Condensed Matter. 2004;16(25):1-31. doi:10.1088/0953-8984/16/25/R01

23. Saisa, Agusnar H, Alfian Z, Nainggolan I. Polymer of Chitosan with ZnO Addition to Optimize High Responsivity and Sensitivity in Sensor Film. AIP Conf Proc. 2020;2267(September):1-8. doi:10.1063/5.0016439

24. Reghioua A, Barkat D, Jawad A, Abdulhameed AS, Rangabhashiyam S, Khan MR, AlOthhman ZA. Magnetic Chitosan-Glutaraldehyde/Zinc Oxide/Fe3O4 Nanocomposite: Optimization and Adsorptive Mechanism of Remazol Brilliant Blue R Dye Removal. J Polym Environ. 2021:1-16. doi:10.21203/rs.3.rs-450675/v1

25. Qiu B, Xu X feng, Deng R hui, Xia G qing, Shang X fu, Zhou P hu. Construction of chitosan/ZnO nanocomposite film by in situ precipitation. Int J Biol Macromol. 2019;122:82-87. doi:10.1016/j.ijbiomac.2018.10.084

26. Wang J. Analytical Electrochemistry. 2nd ed. New York: John Wiley & Sons; 2001. doi:10.5860/choice.38-5590

27. Elgrishi N, Rountree KJ, McCarthy BD, Rountree ES, Eisenhart TT, Dempsey JL. A Practical Beginner’s Guide to Cyclic Voltammetry. J Chem Educ. 2018;95(2):197-206. doi:10.1021/acs.jchemed.7b00361

28. Kundu M, Rajesh, Krishnan P, Gajjala S. Comparative Studies of Screen-Printed Electrode Based Electrochemical Biosensor with the Optical Biosensor for Formaldehyde Detection in Corn. Food Bioproc Tech. 2021;14(4):726-738. doi:10.1007/s11947-021-02604-3

29. Chou TC, Chang CC, Yu HL, Yu WY, Dong CL, Velasco-Vélez JJ, Chuang CH, Chen LC, Lee JF, Chen JM, Wu HL. Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO2 Reduction to Ethylene. J Am Chem Soc. 2020;142(6):2857-2867. doi:10.1021/jacs.9b11126

30. Rivaldi MH, Rizky A, Hardian A, Murniati A. Study of Aluminum-Copper Electrodes for Chromium and Chemical Oxygen Demand Removal from Tannery Wastewater by Electrocoagulation. Jurnal Riset Kimia. 2025;16(1):33-44. doi:10.25077/jrk.v16i1.744

31. Farshchi F, Hasanzadeh M, Feyziazar M, Saadati A, Hassanpour S. Electropolymerization of Chitosan in The Presence Of Cunps on The Surface of A Copper Electrode: An Advanced Nanocomposite for The Determination of Mefenamic Acid and Indomethacin in Human Plasma Samples and Prevention of Drug Poisoning. Analytical Methods. 2020;12(9):1212-1217. doi:10.1039/c9ay02789k

32. Murniati A, Buchari B, Gandasasmita S, Nurachman Z, Hardian A, Triani D. Immobilization of Crude Polyphenol Oxidase Extracts from Apples on Polypyrrole as a Membrane for Phenol Removal. Jurnal Kimia Sains dan Aplikasi. 2021;24(2):62-69. doi:10.14710/jksa.24.2.62-69

33. Murniati A, Buchari B, Gandasasmita S, Nurachman Z. Synthesis and Characterization of Polypyrrole Polyphenol Oxidase (PPy/PPO) on Platinum Electrode. Res J Pharm Biol Chem Sci. 2012;3(4):1-10.

34. Murniati A, Buchari B, Gandasasmita S, Nurachman Z. Sintesis dan Karakterisasi Elektroda Kerja Kasa Baja Dengan Metode Voltammetri Siklik. 2012;13(3):210-215.

35. Vellingiri K, Deep A, Kim KH, Boukhvalov DW, Kumar P, Yao Q. The Sensitive Detection of Formaldehyde in Aqueous Media Using Zirconium-Based Metal Organic Frameworks. Sens Actuators B Chem. 2017;241:938-948. doi:10.1016/j.snb.2016.11.017

36. Kundu M, Bhardwaj H, Pandey MK, Krishnan P, Kotnala RK, Sumana G. Development of Electrochemical Biosensor based on CNT–Fe3O4 Nanocomposite to Determine Formaldehyde Adulteration in Orange Juice. J Food Sci Technol. 2019;56(4):1829-1840. doi:10.1007/s13197-019-03635-7

37. Murniati A, Nur IH, Gumelar N, Budiman S, Buchari B, Gandasasmita S, Nurachman Z. Evaluation of Scan Rate Influence on Cyclic Voltammograms of Copper Electrodes Coated with PS-CS-GA/ZnO Nanocomposite. Jurnal Kartika Kimia. 2024;7(1). doi:10.26874/jkk.v7i1.256

38. Aprillianti RN, Rahayu M, Hardian A, Murniati A. Effect of Polyethylene Glycol Concentration on the Structural and Mechanical Properties of Polysulfone-Based Membranes. Journal of Chemistry and Environment. October 2024:25-38. doi:10.56946/jce.v3i2.469

39. Murniati A, Shardi S, Fauzi I, Hardian A, Ibrahim RM, Buchari B, Gandasasmita S, Nurachman Z. Immobilization of Crude Polyphenol Oxidase Purple Eggplant Extract on Chitosan Membrane for Removal of Phenol Wastewater. European Chemical Bulletin. 2022;11(10):117-125. doi:10.31838/ecb/2022.11.10.016

40. Gunawan AF, Hardian A, Murniati A. Cyclic Voltammetry Study of the Influence of Concentration of K3[Fe(CN)6] and Glucose on Glassy Carbon Electrode. ALCHEMY Jurnal Penelitian Kimia. 2025;21(1):43-52. doi:10.20961/alchemy.21.1.87604.43-52

41. Bard AJ, Faulkner LR. Electrochemical Methods: Fundamentals and Applications. 2nd ed. New York: John Wiley & Sons; 2001. doi:10.1038/s41929-019-0277-8

42. Nisa U, Iswantini D, Ahmad SN, Mahat MM, Putra BR, Saskito DIB, Wahyuni WT. Nonenzymatic Sensor Based on Glassy Carbon Electrode Modified by Platinum Nanoparticles Decorated Reduced Graphene Oxide for Glucose Detection in Human Urine. Jurnal Kimia Valensi. 2024;10(2):215-228. doi:10.15408/jkv.v10i2.40035