Explanation based on thermodynamic parameters regarding effect of sensing film thickness and amount of graphene oxide on sensor performance in aniline, N-phenylglycine and graphene oxide based electrochemical heavy metal ion sensor

Authors

  • Kusumita Dutta Department of Chemical Engineering, National Centre for Flexible Electronics, Indian Institute of Technology Kanpur, Kanpur, UP, India
  • Siddhartha Panda Department of Chemical Engineering, National Centre for Flexible Electronics, Indian Institute of Technology Kanpur, Kanpur, UP, India

DOI:

https://doi.org/10.18203/issn.2454-2156.IntJSciRep20241592

Keywords:

Heavy metal, Partition coefficient, Enthalpy, Reorganization energy, Square wave voltammetry, Barrier width , Solvated ionic radius

Abstract

Background: To construct a heavy metal ion sensor, selectivity and sensitivity are the key important parameters to be taken care of. In our earlier work, film thickness and amount of graphene oxide (GO) content in a novel composite ANGO, synthesized from aniline, N-phenylglycine and GO was varied and sensing parameters including sensitivity, limit of detection (LOD), thermodynamic parameter which includes -∆Gad and charge transport parameter including barrier width (BW), d, of charge transfer based on Simmon’s model were evaluated and compared and an LOD of 800 ppt for Cd2+ was achieved using square wave voltammetry (SWV) withstanding interference from several ions.

Methods: In this work, thermodynamic factors such as -∆Gad, ∆H, reorganization energy, partition coefficient and solvated ionic radius were used to explain the sensor performance with respect to film thickness and amount of GO. All the parameters were analyzed for different film thicknesses and amount of GO and a correlation was achieved. Finally, effect of electrochemical surface area of different polyaniline-based material on thermodynamic properties of detection process of Cd2+ was studied.    

Results: The variation of the thermodynamic properties for Cd2+ sensing with respect to film thickness and amount of GO were examined. Similarly, variation of thermodynamic properties for polyaniline based different sensing materials were examined. Correlation coefficients were developed from the thermodynamic parameters and the d values to explain the underlying mechanism behind improved sensor performance. 

Conclusions: This study can provide information on the thermodynamic properties which can be predicted from BW technique.  The correlation coefficients would help in designing polyaniline based novel sensing film material with the need of lesser number of experiments.

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References

Adhawiyah RE, Lee J. Enhancing Sensitivity and Selectivity: Morphological Modification and Chemical Functionalization within Confined Structures. Int J Precision Engineering Manufacturing. 2024;25(4):875-95.

Gao F, Chunxiu L, Lichao Z, Tiezhu L, Zheng W, Zixuan S, et al. Wearable and flexible electrochemical sensors for sweat analysis: a review. Microsyst Nanoeng. 2023;9(1):1-21.

Montmeat P, Pijolat C, Tournier G, Viricelle JP. The influence of a platinum membrane on the sensing properties of a tin dioxide thin film. Sens Actuators B Chem. 2002;84(2):148-59.

Dutta K, Panda S. Thermodynamic and Charge Transport Studies for the Detection of Heavy Metal Ions in Electrochemical Sensors Using a Composite Film of Aniline, N-phenylglycine and Graphene Oxide. J Electrochem Soc. 2019;166(14):B13355.

Vilan A. Analyzing Molecular Current-Voltage Characteristics with the Simmons Tunneling Model: Scaling and Linearization. J Physical Chemistry C. 2007;111(11):4431-44.

Akkerman HB, Naber RCG, Jongbloed B, Van Hal PA, Blom PWM, De Leeuw DM, et al. Electron tunneling through alkanedithiol self-assembled monolayers in large-area molecular junctions. Proceedings National Academy Sci. 2007;104(27):11161-6.

Hill CM, Kim J, Bard AJ. Electrochemistry at a Metal Nanoparticle on a Tunneling Film: A Steady-State Model of Current Densities at a Tunneling Ultramicroelectrode. J Am Chem Soc. 2015;137(35):11321-6.

Hill CM, Kim J, Bodappa N, Bard AJ. Electrochemical Nonadiabatic Electron Transfer via Tunneling to Solution Species through Thin Insulating Films. J Am Chem Soc. 2017;139(17):6114-9.

Solak AO, Eichorst LR, Clark WJ, McCreery RL. Modified Carbon Surfaces as ‘Organic Electrodes’ That Exhibit Conductance Switching. Anal Chem. 2003;75(2):296-305.

Tseng SH, Peng-Chung JJ, Chuan-Mei T, Tsai-Mu C, Hsueh-Liang C, Yu-Chuan C, et al. Ni2+-Enhanced Charge Transport via π-π Stacking Corridor in Metallic DNA Biophys J. 2011;100(4):1042-48.

Khoshroo M, Rostami AA, Yeganegi S. Cyclic voltammetric and computational study of a 4-bromophenyl monolayer on a glassy carbon electrode. Monatshefte für Chemie-Chemical Monthly. 2008;139(7):781-7.

Sharp KA. Calculation of electron transfer reorganization energies using the finite difference Poisson-Boltzmann model. Biophys J. 1998;74(3):1241-50.

Eckermann AL, Feld DJ, Shaw DJ, Meade TJ. Electrochemistry of redox-active self-assembled monolayers. Coord Chem Rev. 2010;254(15-16):1769-802.

Marcus RA. Tight-binding approximation for semi-infinite solids. Application of a transform method and of delta function normalization. J Chem Phys. 1993;98(7):5604-11.

Gosavi S, Marcus RA. Nonadiabatic Electron Transfer at Metal Surfaces. J Phys Chem B. 2000;104(9):2067-72.

Miller NE, Wander MC, Cave RJ. A Theoretical Study of the Electronic Coupling Element for Electron Transfer in Water. J Phys Chem A. 1999;103(8):1084-93.

Cave RJ, Newton MD. Calculation of electronic coupling matrix elements for ground and excited state electron transfer reactions: Comparison of the generalized Mulliken–Hush and block diagonalization methods. J Chem Phys. 1997;106(22):9213-26.

Marcus RA. Chemical and Electrochemical Electron-Transfer Theory. Annu Rev Phys Chem. 1964;15(1):155-96.

Newton MD, Sutin N. Electron Transfer Reactions in Condensed Phases. Annu Rev Phys Chem. 1984;35(1):437-80.

Johanson G. Modeling of Disposition. Comprehensive Toxicol. 2010;153-77.

Dearden J, Bresnen G. Thermodynamics of Water-octanol and Water-cyclohexane Partitioning of some Aromatic Compounds. Int J Mol Sci. 2005;6(1):119-29.

Papamichael EM, Stamatis H, Stergiou PY, Foukis A, Gkini OA. Enzyme Kinetics and Modeling of Enzymatic Systems. Adv Enzyme Technol. 2019;71-104.

Dutta K, Panda S. Estimation of thermodynamics properties as a measure of the extent of interference in a conducting polymer based electrochemical aqueous ion sensor. Int J Scientific Rep. 2024;10(4):102-10.

Dutta K, Panda S. Identification of the Levels of Interference of Ions toward Heavy Metal Detection in Electrochemical Sensors Using the Barrier Width Technique. J Electrochem Soc. 2018;165(9):B378.

Houchins G, Pande V, Viswanathan V. Mechanism for Singlet Oxygen Production in Li-Ion and Metal-Air Batteries. ACS Energy Lett. 2020;5(6):1893-9.

Bard AJ, Faulkner LR, White HS. Electrochemical methods: fundamentals and applications, 2nd ed. John Wiley and Sons. 2022.

Dutra LMU, Ribeiro MENP. Binary mixture micellar systems of F127 and P123 for griseofulvin solubilization. Polímeros. 2015;25(5):433-9.

Mobasherpour I, Salahi E, Pazouki M. Comparative of the removal of Pb2+, Cd2+ and Ni2+ by nano crystallite hydroxyapatite from aqueous solutions: Adsorption isotherm study. Arab J Chem. 2012;5(4):439-46.

Al Hamouz OCS, Ali SA. Removal of Zinc and Cadmium Ions Using a Cross-linked Polyaminophosphonate. J Macromolecular Sci Part A. 2013;50(4):375-84.

Chen SB, Ma YB, Chen L, Xian K. Adsorption of aqueous Cd2+, Pb2+, Cu2+ ions by nano-hydroxyapatite: Single- and multi-metal competitive adsorption study. Geochem J. 2010;44(3):233-9.

Nightingale ER. Phenomenological Theory of Ion Solvation. Effective Radii of Hydrated Ions. J Phys Chem. 1959;63(9):1381-7.

Jnr MH, Spiff AI, Abia A. Studies on the Influence of Mercaptoacetic Acid (MAA) Modification of Cassava (Manihot sculenta Cranz) Waste Biomass on the Adsorption of Cu 2+ and Cd 2+ from Aqueous Solution. Bull Korean Chem Soc. 2004;25(7):969-76.

Kumar PS, Ramakrishnan K, Kirupha SD, Sivanesan S. Thermodynamic and kinetic studies of cadmium adsorption from aqueous solution onto rice husk. Brazilian J Chem Engineering. 2010;27(2):347-55.

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Published

2024-06-03

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Original Research Articles