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Hydrophobic laser-induced graphene potentiometric ion-selective electrodes for nitrate sensing

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Abstract

Current solid-contact ion-selective electrodes (ISEs) suffer from signal-to-noise drift and short lifespans partly due to water uptake and the development of an aqueous layer between the transducer and ion-selective membrane. To address these challenges, we report on a nitrate ISE based on hydrophobic laser-induced graphene (LIG) coated with a poly(vinyl) chloride–based nitrate selective membrane. The hydrophobic LIG was created using a polyimide substrate and a double lasing process under ambient conditions (air at 23.0 ± 1.0 °C) that resulted in a static water contact angle of 135.5 ± 0.7° (mean ± standard deviation) in wettability testing. The LIG–ISE displayed a Nernstian response of − 58.17 ± 4.21 mV dec−1 and a limit-of-detection (LOD) of 6.01 ± 1.44 µM. Constant current chronopotentiometry and a water layer test were used to evaluate the potential (emf) signal stability with similar performance to previously published work with graphene-based ISEs. Using a portable potentiostat, the sensor displayed comparable (p > 0.05) results to a US Environmental Protection Agency (EPA)–accepted analytical method when analyzing water samples collected from two lakes in Ames, IA. The sensors were stored in surface water samples for 5 weeks and displayed nonsignificant difference in performance (LOD and sensitivity). These results, combined with a rapid and low-cost fabrication technique, make the development of hydrophobic LIG–ISEs appealing for a wide range of long-term in situ surface water quality applications.

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Funding

We gratefully acknowledge funding support from the National Institute of Food and Agriculture, U.S. Department of Agriculture, award numbers 2019–05855, 2020–04109, and 2018–672-67016–27578 awarded as a Center of Excellence. The National Science Foundation under award numbers CBET-1706994, CBET-1756999, CBET-1805512, ECCS-1841649, and CMMI-2037026. We also gratefully acknowledge Leigh Ann Long and the Water Quality Research Lab (WQRL) at Iowa State University for analyzing water samples.

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Authors and Affiliations

  1. Department of Mechanical Engineering, Iowa State University, Ames, IA, 50011, USA

    Robert G. Hjort, Raquel R. A. Soares, Bolin Chen, Bryan Van Belle, Jonathan C. Claussen & Carmen L. Gomes

  2. Department of Chemistry, Iowa State University, Ames, IA, 50011, USA

    Jingzhe Li & Emily Smith

  3. The Ames Laboratory, U.S. Department of Energy, Ames, IA, 50011, USA

    Jingzhe Li & Emily Smith

  4. Materials Analysis and Research Laboratory, Iowa State University, Ames, IA, 50011, USA

    Dapeng Jing

  5. Department of Agricultural and Biological Engineering, Iowa State University, Ames, IA, 50011, USA

    Lindsey Hartfiel & Michelle Soupir

  6. Agricultural Sciences Department, Clemson University, Clemson, SC, 29634, USA

    Eric McLamore

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  1. Robert G. Hjort
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604_2022_5233_MOESM1_ESM.docx

Supplementary file 1 Additional SEM images; XPS and Raman spectra ofLIG after the first laser treatment (e.g., hydrophilic LIG); Table of Ramanspectroscopy ID/IG ratios after second laser treatment;Representative CV figure of bare hydrophobic LIG; Representative emf responsefigure; Representative chronopotentiometry response figure; Equations used for electroactivesurface area, capacitance, selectivity coefficients, and activity valuescalculations; Calibration curves in surface water; Table with results fromsurface water sample analysis using EPA analytical method and LIG-ISEs analysis,and Table of comparison of recently published reports on nitrate ISE. (DOCX 1414 KB)

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Hjort, R.G., Soares, R.R.A., Li, J. et al. Hydrophobic laser-induced graphene potentiometric ion-selective electrodes for nitrate sensing. Microchim Acta 189, 122 (2022). https://doi.org/10.1007/s00604-022-05233-5

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