4.6 Article

Lignosulfonate-Based Conducting Flexible Polymeric Membranes for Liquid Sensing Applications

Journal

MATERIALS
Volume 14, Issue 18, Pages -

Publisher

MDPI
DOI: 10.3390/ma14185331

Keywords

lignosulfonate; potentiometric sensors; carbon nanotubes; conducting polymer; electrical conductivity; transition metals; graphene; ionic liquid

Funding

  1. project CICECO-Aveiro Institute of Materials [UIDB/50011/2020, UIDP/50011/2020]
  2. CESAM [UIDP/50017/2020, UIDB/50017/2020]
  3. i3N by Portuguese Foundation for Science and Technology (FCT)/Ministry of Science, Technology and Higher Education (MCTES) [UIDB/50025/2020, UIDP/50025/2020]
  4. FCT
  5. European Social Fund (ESF) through the Programa Operacional Regional do Centro (Centro 2020) [SFRH/BD/121275/2016]
  6. Fundação para a Ciência e a Tecnologia [SFRH/BD/121275/2016] Funding Source: FCT

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Lignosulfonate-based polyurethanes doped with multiwalled carbon nanotubes were synthesized and utilized as a sensitive material for all-solid-state potentiometric chemical sensors. These sensors exhibited a near-Nernstian or super-Nernstian response to various transition metals and redox pairs. Unlike other lignin-based sensors, the LS-based polymeric membrane did not show irreversible complexation with Hg(II).
In this study, lignosulfonate (LS) from the acid sulfite pulping of eucalypt wood was used to synthesize LS-based polyurethanes (PUs) doped with multiwalled carbon nanotubes (MWCNTs) within the range of 0.1-1.4% w/w, yielding a unique conducting copolymer composite, which was employed as a sensitive material for all-solid-state potentiometric chemical sensors. LS-based PUs doped with 1.0% w/w MWCNTs exhibited relevant electrical conductivity suitable for sensor applications. The LS-based potentiometric sensor displayed a near-Nernstian or super-Nernstian response to a wide range of transition metals, including Cu(II), Zn(II), Cd(II), Cr(III), Cr(VI), Hg(II), and Ag(I) at pH 7 and Cr(VI) at pH 2. It also exhibited a redox response to the Fe(II)/(III) redox pair at pH 2. Unlike other lignin-based potentiometric sensors in similar composite materials, this LS-based flexible polymeric membrane did not show irreversible complexation with Hg(II). Only a weak response toward ionic liquids, [C(2)mim]Cl and ChCl, was registered. Unlike LS-based composites comprising MWCNTs, those doped with graphene oxide (GO), reduced GO (rGO), and graphite (Gr) did not reveal the same electrical conductivity, even with loads up to 10% (w/w), in the polymer composite. This fact is associated, at least partially, with the different filler dispersion abilities within the polymeric matrix.

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